Compounds, polymers of them, processes for the preparation of both, and compositions containing the compounds

ABSTRACT

The first aspect of the invention provides a novel compound containing a reactive functional group represented by formula (1) 
     
         R.sup.2 --O--CO--NH--CH═CH--R.sup.1                    (1) 
    
     wherein R 1  represents a hydrogen atom, an aromatic hydrocarbon group, or a saturated or unsaturated aliphatic hydrocarbon group, R 2  represents a formula comprising alicyclic functionality. 
     The second aspect provides an active energy ray-curable unsaturated resin composition prepared by mixing a reaction product of the above-mentioned compound (1) with an unsaturated resin containing an acid group and with a diluent. The composition can be cured by active energy rays, and it can be used as an alkali developable and active energy ray-curable type resist resin composition. 
     The third aspect provides an active energy ray-polymerizable unsaturated resin composition obtainable by allowing to react an unsaturated compound (E) containing an alicyclic epoxy group represented by formula (1) with a colloidal silica (F) in the presence of a metal chelate and/or metal alkoxide (G). A powder-state active energy ray-polymerizable unsaturated resin composition is obtained by removing a solvent from the composition. 
     A fourth aspect of the invention provides a composition which comprises a copolymer of a specified polysiloxane-based macromonomer with a compound represented by formula (1), and an organic aluminum chelate compound, and the composition is curable at low-temperatures.

TECHNICAL ART OF FIRST ASPECT OF THE INVENTION

First aspect of the invention relates to a novel compound containing areactive functional group and the use thereof. In more detail, itrelates to a novel compound which readily polymerizes solely orcopolymerizes by heating or light irradiation, and which can be employedas a printing use, a resist for electronics, a coating, and an adhesive,etc.

BACKGROUND ART OF FIRST ASPECT OF THE INVENTION

There has been desired an improvement of dissolution degree in aphotosensitive film, etc. with a progress of uses for a variety ofprinting plates and electronics. As a result pulled by such the marketneeds, a polymer industry remarkably progresses, and there are developedand employed a great variety of compounds and polymeric materials over awide scope. In recent years, there has been particularly desired adevelopment of more excellent compounds and polymeric materials with theprogress of a shift to high function and performance in industrialproducts.

For example, in a field of resists for a printed circuit board, as amethod for forming a resist in the printed circuit board, there has beendeveloped a photographic method in which a desired resist pattern isformed by exposing a photosensitive film using a fixed pattern to lightand by developing it.

Further, there has been employed a liquid-state resist from a viewpointof price or characteristics not existing in the photosensitive film.

Still further, as a developing agent in the case of forming a resist,there have been conventionally employed a solvent-developing type and adiluted aqueous alkali solution-developing type in which there isemployed a sodium carbonate aqueous solution, and a development isshifting to the use of the diluted aqueous alkali solution-developingtype in view of a break of ozone gas layer and the influence on workingsurroundings.

Under such the market needs, there have been developed a compound havingat least two reactive groups in the molecule, and a reactive oligomer orpolymer having a plurality of reactive groups which are side chains fora thermosetting or photo-curable resin. In addition, there areinvestigated and developed a wide range of industrial uses in a varietyof fields, and there is expected a development of new materials asfunctional resins other than those. Particularly, there are desiredeagerly a development of a multi-functional monomer capable ofpolymerizing solely or copolymerizing with other compound containingunsaturated groups by heating or by irradiating the light such as anultraviolet ray or an ionic radioactive ray, and a development of amonomer or a polymer which composes a curable resin which is employedfor printing uses and as a resist for electronics, a coating, and anadhesive, etc. Particularly, there is desired eagerly a development of amonomer or a polymer therefrom which composes a resist which has a shortdeveloping time, and which is excellent in sensitivity, adhesion, heatresistance in a solder and, moreover hydrolysis resistance.

DISCLOSURE OF FIRST ASPECT OF THE INVENTION

The present inventors, as a result of a repeated intensive investigationfor attaining the above-mentioned purposes, have found that a compoundor a polymer having a specified structure has a photo-curability orthermosetting property, whereby, the above-mentioned purposes can beattained, and the present invention was completed.

That is, the present invention provides a compound represented byformula (1). Further, there is provided the compound characterized inthat a group including a reactive functional group is a group includingan alicyclic epoxy group.

Still further, there is provided the compound characterized in that thealiphatic hydrocarbon group substituted by a group including a reactivefunctional group is a group represented by formula (2) or (3). Also,there is provided a polymer of the compound. In addition, there isprovided a process for the preparation of a compound represented byformula (1) which comprises allowing to react a compound having ahydroxyl group represented by formulae (4-1) or (4-2) with a compoundrepresented by formula (5). Hereinafter, the present invention isillustrated in detail.

    --R.sup.2 --O--CO--NH--CH═CH--R.sup.1                  (1)

(in the formula, R¹ represents a hydrogen atom, an aromatic hydrocarbongroup, or a saturated or unsaturated aliphatic hydrocarbon group, R²represents an aliphatic hydrocarbon group substituted by a groupincluding a reactive functional group) ##STR1## (in the formula, R⁴ andR⁵ represent a hydrogen atom, a methyl group or ethyl group,respectively, "m" is an integer of 4-8, and "n" is an integer of 1-10)##STR2## (in the formula, R⁴ and R⁵ represent a hydrogen atom, a methylgroup or ethyl group, respectively, "m" is an integer of 4-8, and "n" isan integer of 1-10)

    N.sub.3 --CO--CH═CH--R.sup.1                           (5)

(in the formula, R¹ represents a hydrogen atom, an aromatic hydrocarbongroup, or a saturated or unsaturated aliphatic hydrocarbon group).

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is an IR chart of 3,4-epoxycyclohexylmethyl oxycarbonylvinylamine(compound A) obtained in Example 1, and

FIG. 2 is an IR chart of a polymer (polymer A) from the compound Aobtained in Example 4.

BEST MODE FOR CARRYING OUT THE FIRST ASPECT OF THE INVENTION

In the compound represented by the formula (1) of the present invention,R¹ is preferably a hydrogen atom, an aromatic hydrocarbon group, or asaturated or unsaturated aliphatic hydrocarbon group.

In the case of the aromatic hydrocarbon group, a phenyl group and benzylgroup are preferred. Further, in the case of the saturated aliphatichydrocarbon group, an alkyl group having a carbon number of 1-10 ispreferred. Still further, in the case of the unsaturated aliphatichydrocarbon group, there are particularly preferred vinyl group, allylgroup, and a (meth)acrylic group. Of those, particularly, R¹ is mostpreferably a hydrogen atom, methyl group, ethyl group, and phenyl group.

R² represents an aliphatic hydrocarbon group substituted by a groupincluding a reactive functional group and, in particular, it ispreferably a group represented by the above-mentioned formula (2) or(3). It is to be noted that in the formula (3), R⁴ and R⁵ are a hydrogenatom, a methyl group or ethyl group, respectively, "m" is preferably aninteger of 4-8, and "n" is preferably an integer of 1-10.

The compound represented by the formula (1) can be prepared by allowingto react, for example, a compound having a hydroxyl group represented byformula (4-1) or (4-2) with a compound represented by the formula (5).Herein, the compound having a hydroxyl group represented by the formula(4-1) is 3,4-epoxycyclohexylmethyl alcohol. Also, the compound having ahydroxyl group represented by the formula (4-2) is a lactone polymerwhich can be prepared by polymerizing 1-10 mol of a lactone with3,4-epoxycyclohexylmethyl alcohol. The compound having a hydroxyl grouprepresented by the formula (4-2) can be prepared by a ring-openingpolymerization of, specifically, ε-caprolactone using an initiator whichis a compound having an active hydrogen such as the compound (4-1) whichis an alcohol.

As the lactone, in addition to ε-caprolactone, valerolactone may be alsopolymerized solely or copolymerized with ε-caprolactone, etc.

On the other hand, the compound represented by the formula (5) can beprepared by allowing to react an aqueous solution of alkali or alkaliearth metal salts typified by, for example, sodium azide which is ametal azide with R¹ --CH═CH--COCl which is an acid chloride. As the R¹,the same group R¹ is employed as in the compound represented by theformula (1) which is a desired product.

In the reaction of the metal azide with the acid chloride, the acidchloride is preferably allowed to react in reaction ratio of 0.01-1.5mol based on 1 mol of the metal azide. The reaction is conducted byadding dropwise a solution of the acid chloride into an aqueous solutionof the metal azide. Solvents for the acid chloride are not particularlylimited, and there are preferred ketones such as acetone and methylethylketone. Also, although dropwise addition of the metal azide into anaqueous solution can be conducted at temperature of from -78 to 100° C.,it is preferably conducted at a room temperature or lower temperaturesin view of stability of the metal azide.

The compound represented by the formula (1) is usually prepared byallowing to react generally 0.5-10.0 mol of the compound having ahydroxyl group represented by the formula (4-1) or (4-2) with 1 mol of acompound represented by the formula (5).

The reaction temperature is preferably 0 to 150° C. in view of arelationship between a stability of the compound represented by theformula (5) and the reaction temperature. In the reaction, a catalystcan be employed. As the preferred catalysts, there can be exemplified atertiary amine such as triethyl amine and dimethylbenzyl amine, aquaternary amine such as tetraethyl ammonium chloride, and phosphinessuch as triphenyl phosphine.

The compound represented by the formula (1) can be polymerized solely orcopolymerized with other compound having a polymerizable unsaturatedgroup owing to a carbon--carbon double bond in the molecule. Aspolymerization processes, there are exemplified a solutionpolymerization, an emulsion polymerization, a suspension polymerization,and a sedimentation polymerization, and a solution radicalpolymerization is most convenient.

Copolymerizable monomer is not particularly limited, if it is a compoundhaving a polymerizable unsaturated group, and there are exemplified thefollowing monomers. Specifically, as alkyl(meth)acrylates, there aremethyl(meth)acrylates, ethyl(meth)acrylates, propyl(meth)acrylates,butyl(meth)acrylates, pentyl(meth)acrylates, and hexyl(meth)acrylates,and the like. Further, as alkyl(meth)acrylates having hydroxyl group,there are 2-hydroxyethyl(meth)acrylates, hydroxypropyl(meth)acrylates,hydroxybutyl(meth)acrylates, and a caprolactone-modified2-hydroxyethyl(meth)acrylates, and the like. Still further, as other(meth)acrylates, there are exemplified methoxydiethyleneglycol(meth)acrylate, ethoxydiethyleneglycol(meth)acrylate,isooctyloxydiethyleneglycol(meth)acrylate, phenoxytriethyleneglycol(meth)acrylate, methoxytriethyleneglycol(meth)acrylate, andmethoxypolyethyleneglycol(meth)acrylate, and the like, and further, asother monomers, there are styrenes, and the like.

As a polymerization initiator to be employed for obtaining the polymerof the present invention, there can be employed initiators which areusually employed for polymerization of the compound having apolymerizable unsaturated group.

As specific examples, there can be exemplified peroxide-based compoundssuch as lauroyl peroxide, di-t-butyl peroxide,bis(4-t-butylcyclohexyl)peroxydicarbonate,t-butylperoxy(2-ethylhexanoate), methylethylketone peroxide, benzoylperoxide, and cumenhydroperoxide, azo-based compounds such as 2,2-azobisisobutylonitrile and 2,2'-azobis-(2,4-dimethylvaleronitrile).

Further, the peroxide-based compounds and azo-based compounds may bealso employed by mixing with each other.

In polymerization reaction, a polymerization solvent can be employed,and it is not particularly limited, if it can dissolve the monomers andthe polymers. For example, there are employed aromatic hydrocarbons suchas benzene, toluene, and xylene, alcohols such as methylalcohol,ethylalcohol, and 2-propanol, ketones such as acetone,methylethylketone, and methyl isobutylketone, ethers such asdiethylether, dibutylether, and dioxane, acetates such as ethyl acetate,isobutyl acetate, and ethyleneglycol monoalkylether acetates,diethyleneglycol monoalkylether acetates, amides such asdimethylformamide and dimethylacetamide, halogenated hydrocarbons suchas carbon tetrachloride and chloroform, and the like. The solvents maybe employed solely or in combination. A number average molecular weightin polymers or copolymers obtained usually ranges from 5,000 to 500,000,preferably 10,000 to 80,000 based on a standard polystyrene with a GPC.

The compound (1) of the present invention, a homopolymer thereof, and acopolymer thereof are mixed with other resins, ring-opening additioncatalysts for an epoxide, monomers or oligomers for dilution,photo-initiators, and other additives to obtain a curable resincomposition which can be employed as a resist by photo-curing orthermally-curing.

In the other resins which can be mixed with the compound (1) of thepresent invention or the polymer thereof, an acid value preferablyranges from 50 to 150 KOHmg/g. In the case that the acid value is lessthan 50 KOHmg/g, it is difficult to sufficiently remove an uncured resincomposition by a diluted aqueous alkali solution and, in the case thatthe acid value exceeds 150 KOH mg/g, moisture resistance and electricproperties become occasionally poor in a cured layer. Further, a weightaverage molecular weight in the resin to be mixed preferably ranges from5,000 to 150,000. However, the range is different according to uses, andin uses such as a solder resist or etching resist, etc. in which thethickness of a coating layer is not more than 30 μm, a weight averagemolecular weight preferably ranges from 10,000 to 40,000 in view of arequirement of an excellent developability. Still further, in uses suchas a printing plate, etc. in which the thickness of a coating layer is100 μm or so, a weight average molecular weight preferably ranges from100,000 to 150,000 or so because of attaching importance to sensitivity.In the case that the weight average molecular weight exceeds 150,000,developability remarkably lowers, and there is occasionally also causeda problem that storage stability becomes poor.

As ring-opening addition catalysts for an epoxide capable of mixing withthe compound (1) of the present invention and polymer thereof, there canbe exemplified a tertiary amine such as dimethylbenzyl amine, triethylamine, tetramethyl ethylenediamine, and tri-n-octyl amine, a quaternaryamine such as tetramethyl ammonium chloride, tetramethyl ammoniumbromide, and tetrabutyl ammonium bromide, an alkyl urea such astetramethyl urea, an alkyl guanidine such as tetramethyl guanidine, andphosphines such as triphenyl phosphine, and salts thereof. Those may beemployed solely or in combination of two or more kinds. These catalystsare preferably employed in an amount of 0.01-10% by weight, morepreferably 0.5-3.0% by weight based on the compound of the formula (1)which is an epoxy compound, or the (co)polymer thereof. In the case ofless than 0.01% by weight, a catalytic effect is low and, in the casethat the amount exceeding 10% by weight is added, curability becomespoor.

As monomers or oligomers for dilution capable of mixing with thecompound (1) of the present invention and polymer thereof, there can beexemplified a compound having a radical polymerizable double bondtypified by an acrylate or methacrylate compound, a vinyl aromaticcompound, and an amide-based unsaturated compound, and the like.

As the acrylate or methacrylate, there can be exemplifiedalkyl(meth)acrylates such as methyl(meth)acrylate, ethyl(meth)acrylate,propyl(meth)acrylate, butyl(meth)acrylate, pentyl(meth)acrylate, andhexyl(meth)acrylate, alkyl(meth)acrylates having hydroxyl group such as2-hydroxyethyl(meth)acrylates, hydroxypropyl(meth)acrylates,hydroxybutyl(meth)acrylates, and caprolactone-modified2-hydroxyethyl(meth)acrylates, alkoxy(meth)acrylates such asmethoxydiethyleneglycol(meth)acrylate, ethoxydiethyleneglycol(meth)acrylate, isooctyloxydiethyleneglycol(meth)acrylate,phenoxytriethyleneglycol(meth)acrylate, methoxytriethyleneglycol(meth)acrylate, and methoxypolyeneglycol#400-(meth)acrylate,bifunctional (meth)acrylates such as 1,6-hexanediol di(meth)acrylate andneopentylglycol di(meth)acrylate, trifunctional (meth)acrylates such astrimethylolpropane tri(meth)acrylate, and polyfunctional (meth)acrylatessuch as dipentaerythritol hexaacrylate, and the like. Further, as thevinyl aromatic compound, there can be exemplified styrene, vinyltoluene,and α-methylstyrene, and the like. Still further, as the amide-basedunsaturated compound, there can be exemplified acryl amide and methacrylamide, and the like.

On the other hand, as the oligomers, there can be exemplified(meth)acrylates of a polyester polyol, (meth)acrylates of a polyetherpolyol, an adduct of a polyepoxide to (meth)acrylic acid, and a resin inwhich hydroxy(meth)acrylate is introduced into a polyol through apolyisocyanate, and the like.

The monomers or oligomers for dilution capable of mixing preferablyrange from 0 to 300 parts by weight, particularly, from 10 to 100 partsby weight based on 1 part by weight of the compound of the presentinvention or the polymer of the present invention. In the case that themonomers or oligomers for dilution exceed 300 parts by weight,developability occasionally lowers.

As the photo-polymerization initiator capable of mixing with thecompound (1) of the present invention or the polymer thereof, there canbe exemplified benzophenone, acetophenone, benzyl, benzyldimethylketone, benzoin, benzoin methylether, benzoin ethylether, benzoinisopropylether, dimethoxy acetophenone, dimethoxyphenyl acetophenone,diethoxy acetophenone, and diphenyldisulfide, and the like, and whichmay be employed solely or in mixing of two or more kinds. Thephoto-polymerization initiator can be employed together with, forexample, a tertiary amine which is an agent for giving a synergeticeffect by which there is accelerated conversion of absorbed photo-energyto a free radical for initiating polymerization. It is to be noted thatin the case of curing the compound of the present invention and thepolymer thereof by irradiation of an electronic beam, thephoto-polymerization initiator may also be not mixed.

As the other additives capable of being mixed with the compound (1) ofthe present invention or the polymer thereof, there can be optionallyexemplified an inhibitor for a thermal polymerization, a surface activeagent, a photo-absorbent, a thixotropic agent, a dye, and a pigment, andthe like.

For employing the compound of the present invention and the polymerthereof, a curable resin is coated as a thin layer on a base material,and then cured. As a method for forming the thin layer, there areemployed spraying, brushing, a roll coating, a curtain coating, anelectro-deposition coating, and an electrostatic coating, and the like.Further, in the case that it is employed as a liquid resist or dry film,it is cured by light after coating a curable resin composition on a basematerial. As "light", there can be employed a high pressure mercurylamp, an ultraviolet ray, an EB, and a laser beam, and the like. Stillfurther, in the case that it is employed as one component in a liquidresist, it is also thermally cured. Curing can be conducted atconditions of 100-200° C., and 1-90 minutes.

Although curing is preferably conducted in an atmosphere of an inertgas, it can be also conducted in air atmosphere.

EXAMPLES OF FIRST ASPECT OF THE INVENTION

Hereinafter, although the present invention is specifically illustratedby Examples, the present invention is not limited by those. It is to benoted that "%" represents "% by weight" except particularly showing.

Example 1

Synthesis of 3,4-epoxycyclohexyl methyloxycarbonyl vinylamine)

A separable flask having capacity of 100 ml equipped with an agitator, athermometer, a regulator for reflux, a dropwise funnel, and a tube forsupplying nitrogen was charged 20 ml of aqueous solution containing 2.8mol/liter of sodium azide, followed by adding dropwise 20 ml of acetonesolution containing 2.5 mol/liter of acrylic chloride at 0° C. over 10minutes and by aging for 2 hours. Successively, there were added 3.84 gof 3,4-epoxycyclohexylmethylalcohol ("ETHB" manufactured by DaicelChemical Industries, Ltd.) and 5 ml of triethylamine, followed byallowing to react at 70° C. for 12 hours. From a reaction liquidobtained, 3,4-epoxycyclohexylmethyl oxycarbonylvinylamine (hereinafter,referred to as Compound A) was obtained. Yield was 72%.

There are shown the measurement results of IR and NMR in relation to theCompound A.

(1) IR: 3300 (N--H), 2930 (--CH₂ --, a cycloaliphatic methylene), 1710(C═O), 1640 (vinyl group), 850 (epoxy group) cm⁻¹.

(2) ¹ H-NMR (CDCl₃): δ=0.7-2.5 (m, 7H), 3.17 (s, 2H), 3.91 (dd, 2H,J=2.6 Hz, 6.4 Hz), 4.26 (d, 1H, J=8.2 Hz), 4.49 (d, 1H, J=15.4 Hz), 6.69(dd, 1H, J=8.2 Hz, 15.4 Hz), 7.1 (br. s, 1H).

(3) ¹³ C-NMR (CDCl₃): δ=20.86 (t), 22.76 (d), 23.46 (d), 24.38 (t),26.82 (t), 27.96 (t), 29.58 (t), 32.29 (t), 50.98 (d), 51.53 (d), 52.34(d), 69.08 (t), 93.03 (t), 130.03 (d), 153.81 (s). ##STR3##

Examples 2 and 3

The same operations were followed as in the Example 1, except thatacrylic chloride in the Example 1 was changed to methacrylic chloride toobtain Compound B (Example 2). Also, likewise, the same operations werefollowed as in the Example 1, except that acrylic chloride in theExample 1 was changed to phenylacrylic chloride to obtain Compound C(Example 3). It was identified by measurements with IR and NMR that theCompounds B and C are compounds shown by the following structures. Yieldof the Compound B was 83%, and yield of the Compound C was 74%. ##STR4##

Example 4

Synthesis of a polymer from the Compound A

Under an atmosphere of nitrogen, there were charged 10 ml of benzene,24.6 mg of 2,2'-azobisisobutylonitrile ("AIBN" manufactured by NihonHydrazine, Ltd.), and 985 mg of the Compound A in a sealed tube.Subsequently, temperature was elevated to 70° C., and a polymerizationreaction was conducted for 24 hours. After the reaction, a polymer(hereinafter, referred to as Polymer A) was isolated using abenzene/hexane system. As a result, yield was 72%.

There were conducted an IR measurement, an NMR analysis, and a GPCmeasurement in relation to the Polymer A obtained, and it was identifiedthat the Polymer A is a polymer of the Compound A.

(1) IR (KBr): 3320 (N--H), 2930 (a cycloaliphatic methylene), 1700(C═O), 810 (epoxy group) cm⁻¹.

(2) ¹ H-NMR (CDCl₃): δ=0.8-2.5 (m, 10H), 3.23 (s, 2H), 3.86 (s, 1H), 5.5(gr, s, 1H).

(3) ¹³ C-NMR (CDCl₃): δ=21.07 (t), 22.91 (d), 23.62 (d), 24.54 (t),26.87 (t), 28.17 (t), 29.74 (t), 32.45 (t), 45.78 (d), 51.03 (d), 51.58(d), 52.39 (d), 68.70 (t), 156.19 (s).

GPC (based on Polystyrene); Number average molecular weight (Mn)=39,790,Molecular weight distribution (Mw/Mn)=1.67

Examples 5 and 6

Synthesis of a polymer from the Compound B or C

The same operations were followed as in the Example 4, except that theCompound A in the Example 4 was changed to the Compound B or C. PolymerB was obtained from the Compound B, and Polymer C was obtained from theCompound C.

It was identified that the Polymers B and C are a polymer of theCompounds B and C, respectively, from IR, NMR, and GPC analyses inrelation to the Polymers B and C.

Reference Example

Synthesis of a solution of a resin having carboxylic groups

Into a 2L-separable flask equipped with an agitator, a thermometer, aregulator for reflux, a dropwise funnel, a tube for supplying nitrogengas, there were charged 300 g of dipropyleneglycol monomethylether("MFDG" manufactured by Nihon Nyukazai, Ltd.), and 12.0 g oft-butylperoxy 2-ethylhexanoate ("Perbutyl O" manufactured by NihonYushi, Ltd.) and, after temperature was elevated to 95° C., there wereadded dropwise 172 g of methacrylic acid, 126 g of methylmethacrylate,9.5 g of 2,2'-azobisisobutylonitrile ("ABN-E" manufactured by NihonHydrazine Kogyo, Ltd.), and 200 g of MFDG over 3 hours. After thedropwise addition, aging was conducted for 4 hours to prepare a mainpolymer having carboxylic groups. Subsequently, there were added 202 gof epoxycyclohexyl methylacrylate ("Cyclomer A200" manufactured byDaicel Chemical Industries, Ltd.), 2 g of triphenylphosphine, and 1.0 gof methylhydroquinone to allow to react with the main polymer at 100° C.for 10 hours. Reaction was conducted in a mixed gases atmosphere ofair/nitrogen. By the reaction, there was obtained Resin solution Dhaving an acid value of 100 KOHmg/g, double bond equivalent (the resinweight per 1 mol of unsaturated groups) of 450, and a weight averagemolecular weight of 20,000.

Example 7

Evaluation of a photo-curable resin

The Compound A obtained in the Example 1, the Polymers A, B, and Cobtained in the Examples 4-6, and the Resin solution D obtained in theReference Example were mixed with dipentaerythritol hexaacrylate (DPHA)which is a monomer for dilution, Phthalocyanine Green which is a dye,and 2-methyl-1-[4-(methylthio)phenyl]-2-morfolino-propane-1 ("Irugacure907" manufactured by Ciba-Geigy, AG) which is an initiator by mixingproportion as shown in Table-1 to prepare a photo-curable resincomposition by which an evaluation for a solder resist was conducted.

The solder resists obtained in the Example were coated on a base plateon which a pattern is formed in the thickness of 20-30 μm with abar-coater, followed by drying at 80° C. for 20 minutes with anair-circulation dryer. And then, a negative film was closely contacted,and there was irradiated a beam having 1000 mJ/cm². Further, developingwas conducted with 1% sodium carbonate aqueous solution, and a coatinglayer obtained was dried at 150° C. for 30 minutes in an air-circulationoven to obtain a solder resist layer. There were evaluated developingtime (min), sensitivity, adhesion, heat resistance in soldering, andhydrolysis resistance in the solder resists in the Examples.

Results are shown in Table 1.

Measured items and methods for measuring

(1) Developing time: As the developing time, there was measured adeveloping time in 1% sodium aqueous solution, and it was evaluatedaccording to the following standards. It is to be noted that "soluble ina diluted aqueous alkali solution" means that the developing time isless than 20 seconds. o: less than 20 seconds, ▴: developable within20-60 seconds, x: required exceeding 60 seconds.

(2) Sensitivity: It was evaluated with a Step Tablet manufactured byKodak, Co.

(3) Adhesion: Peeling test using a cellophane tape was conducted inrelation to the resist layer obtained according to JIS D0202. o:100/100, ▴: 50/100-99/100, x: 0/100-49/100.

(4) Heat resistance in a solder: Appearances in a solder resist layerwere visually evaluated after immersed in a solder bath at 260° C. for20 seconds. o: No abnormality in a coating layer, ▴: Blisters andpeeling were slightly observed in a coating layer, x: Blisters andpeeling were observed in a coating layer.

(5) Hydrolysis resistance: After immersed in warm water at 40° C. for 24hours, appearances in a coating layer were visually evaluated forjudgement. o: Quite no change, ▴: Glossiness was slightly lost in acoating layer, x: Glossiness was lost.

                  TABLE 1                                                         ______________________________________                                                  (part by weight)                                                                Example  Example  Example                                                                              Example                                    1 2 3 4                                                                     ______________________________________                                        Polymer A   100                                                                 Polymer B  100                                                                Polymer C   100                                                               Resin solution D 100  100  100  100                                           Compound A    20                                                              DPHA 40  40  40  20                                                           Phthalocyanine Green 2 2 2 2                                                  Irugacure 907 7 7 7 7                                                         Evaluation Result                                                             Developing time (min) O O O O                                                 Sensitivity 7 7 7 7                                                           Adhesion O O O O                                                              Heat resistance in a O O O O                                                  solder                                                                        Hydrolysis resistance O O O O                                               ______________________________________                                    

According to the present invention, there can be provided a novelcompound which is exceedingly useful, and which can be employed for acurable resin composition. The novel compound and a polymer (amulti-functional epoxy resin) therefrom can form a cured layer bycoating on the surface of a metal, and then by irradiating a radiationray such as an ultraviolet ray and an electronic beam. According to thepresent invention, there can be obtained a multi-functional monomer or apolymer therefrom which provides a curable resin composition which isexcellent in adhesion of a coating layer, heat resistance in a solder,and resistance in a weak aqueous alkali, etc.

TECHNICAL FIELD OF SECOND ASPECT OF THE INVENTION

Second aspect of the invention relates to an active energy ray-curabletype resist resin composition containing reactive functional groups andthe uses. In more detail, it relates to an active energy ray-curabletype resist resin composition which can be readily cured by heating orphoto-irradiation, and it can be developed by an alkali.

BACKGROUND ART OF SECOND ASPECT OF THE INVENTION

Heretofore, as an active energy ray-curable type unsaturated resincomposition, there have been developed a variety of compositions andthese are widely utilized in fields of coatings, composite materials,and electronic parts, and the like. Further, it has been recently triedto develop a resin composition which is mainly composed of a vinyl resinas one of the active energy ray-curable type unsaturated resincomposition. Still further, as a composition which is mainly composed ofa vinyl resin, there is presently known a product obtained by a reactionof a vinyl resin having a high acid value with a vinyl compound havingan aliphatic epoxy group.

However, in a coating layer formed from the composition, there are notsufficient an adhesion and water resistance, and it does not showproperties to be sufficiently satisfied in practical uses.

DISCLOSURE OF SECOND ASPECT OF THE INVENTION

The present inventor, as a result of an intensive investigation forsolving the above-mentioned problems, has found that there can be solvedthe above-mentioned problems by an active energy ray-curable typeunsaturated resin composition in which a reaction product of anunsaturated compound which has a specified structure containing acycloaliphatic epoxy group with an unsaturated resin having acid groupsis diluted by an organic solvent and a polymerizable vinyl monomer, andattained a completion of the present invention.

That is, the present invention provides an active energy ray-curabletype unsaturated resin composition which comprises mixing a reactionproduct of an unsaturated compound containing an alicyclic epoxy grouprepresented by formula (6) with an unsaturated resin containing acidgroups, with a diluent.

Further, there is provided the active energy ray-curable typeunsaturated resin composition, wherein the unsaturated resin containingacid groups is an acryl-based resin containing acid groups. Stillfurther, there is provided an alkali developable and active energyray-curable type resist resin composition which comprises the activeenergy ray-curable type unsaturated resin composition. Hereinafter, thepresent invention is illustrated in detail.

    R.sup.2 --O--CO--NH--CH═CH--R.sup.1                    (6)

(in the formula, R¹ represents a hydrogen atom, an aromatic hydrocarbongroup, or a saturated or unsaturated aliphatic hydrocarbon group, R²represents formula (2) or (3)), ##STR5## (in the formula, R⁴ and R⁵represent a hydrogen atom, a methyl group or ethyl group, respectively,"m" is an integer of 4-8, and "n" is an integer of 1-10).

BEST MODE FOR CONDUCTING THE SECOND ASPECT OF THE INVENTION UNSATURATEDCOMPOUND CONTAINING AN ALICYCLIC EPOXY GROUP

The unsaturated compound containing an alicyclic epoxy group to beemployed in the present invention is the compound represented by theabove-mentioned formula (6) and, of the compound of the first aspect ofthe invention represented by the formula (1), it is a compound havingthe same R², and it is prepared by the same method for the preparation,and it has the same structural formula as in the compound represented bythe above-mentioned formula (2) or (3).

The compound represented by the formula (6) to be employed in thepresent invention can be also employed as a copolymer by copolymerizingowing to a carbon-carbon double bond in the molecule with one or morekinds of monomers employed in the acryl-based resin containing acidgroups which is described below.

UNSATURATED RESIN CONTAINING ACID GROUPS

As the unsaturated resin containing acid groups to be employed in thepresent invention, if it is a resin containing at least one ofunsaturated groups and acid groups in the molecule, it may be employedand, for example, there can be exemplified an ethylenic unsaturated acid(co)polymer, an acrylic resin containing acid groups, a modifiedunsaturated monocarboxylic acid, a polyester resin containing acidgroups, a bisphenol A type resin containing acid groups, a novolak resincontaining acid groups, a polyamide acid, and a polyimide containingacid groups. Of those, there are preferred the ethylenic unsaturatedacid (co)polymer and the acryl-based resin containing acid groups.Because a method for the preparation is simple, and resin properties canbe readily controlled.

As the above-mentioned ethylenic unsaturated acid (co)polymer, there canbe exemplified a (co)polymer of maleic anhydride, maleic acid, fumaricacid, and itaconic acid, etc.

As the above-mentioned acryl-based resin containing acid groups, therecan be exemplified a (co)polymer of an acryl-based monomer containingacid group such as acryl-based compounds, for example, acrylic acid,methacrylic acid, carboxymethyl, (meth)acrylate,2-carboxyethyl(meth)acrylate, 2-carboxypropyl(meth)acrylate,2-carboxypropyl(meth)acrylate, crotonic acid, andβ-carboxyethyl(meth)acrylate, and further an adduct of ε-caprolactone to(meth)acrylic acid. Further, as the acryl-based resin containing acidgroups, there can be also employed a copolymer in which theabove-mentioned acryl-based monomer is employed as an essentialcomponent, and there are copolymerized together one kind or more kindsof monomers selected from the following compounds.

As the monomers to be employed herein, there can be exemplified (i)esters of a (meth)acrylic acid, for example, a methyl(meth)acrylate, anethyl(meth)acrylate, a propyl(meth)acrylate, a butyl(meth)acrylate, a2-ethylhexyl(meth)acrylate, a stearyl(meth)acrylate, ahydroxyethyl(meth)acrylate, and a hydroxypropyl(meth)acrylate, and thelike, (ii) an aromatic vinyl compound, for example, styrene,α-methylstyrene, vinyltoluene, and p-chlorostyrene, and the like, (iii)an amide-based unsaturated compound, for example, a (meth)acrylamide,diacetone acrylamide, N-methylolacrylamide, andN-butoxymethylacrylamide, and the like, (iv) a polyolefin-basedcompound, for example, butadiene, isoprene, and chloroprene, and thelike, (v) and others, for example, a (meth)acrylonitrile,methylisopropenyl ketone, vinyl acetate, vinyl propionate, and vinylpivarate, and the like.

As the above-mentioned modified unsaturated monocarboxylic acid, if itis a modified unsaturated monocarboxylic acid containing an unsaturatedgroup and carboxylic group, in which a chain is extended between theunsaturated group and carboxylic acid, it is not particularly limitedand, for example, there can be exemplified an unsaturated monocarboxylicacid having ester bond such as a lactone-modified compound in whichterminal hydroxyl group is modified by an acid anhydride, and a modifiedunsaturated monocarboxylic acid having ether bond, and the like.

It is to be noted that the unsaturated resin containing acid groups tobe employed in the present invention is a resin which is a reactionproduct into which unsaturated groups are introduced, and which isobtained by allowing to react all or partial acid groups in theunsaturated resin with all or partial epoxy groups derived from theunsaturated compound containing an alicyclic epoxy group. Accordingly,it is required that unsaturated groups which are capable of being curedby an active energy ray are introduced into a reaction product obtained,an acid value in the compound is preferably not less than 15 KOHmg/g,and more preferably 40-500 KOHmg/g.

REACTION OF THE UNSATURATED COMPOUND CONTAINING AN ALICYCLIC EPOXY GROUPWITH THE UNSATURATED RESIN CONTAINING ACID GROUPS

The unsaturated compound containing an alicyclic epoxy group representedby the formula (6) is preferably allowed to react with the unsaturatedresin containing acid groups in an amount ranging in 1.08-5 mol ofcarboxylic groups in the unsaturated resin containing acid groups basedon 1 mol of the unsaturated compound containing an alicyclic epoxygroup. Because there sufficiently proceeds a ring-opening additionreaction of epoxy groups with acid groups in the range. It is to benoted that in 100 parts by weight of the unsaturated resin containingalicyclic epoxy groups which is allowed to react with the unsaturatedresin containing acid groups in the present invention, there can be alsoemployed together an unsaturated compound containing an aliphatic epoxygroup such as glycidylmethacrylate, β-methylglycidyl methacrylate, andallylglycidylether, and further, any one of other alicyclic epoxycompounds containing an unsaturated group described hereinafter in arange of 0-90% by weight. As R⁷ in the compounds described hereinafter,there are exemplified linear or branched alkylene groups, that is,methylene, ethylene, propylene, trimethylene, tetramethylene,ethylethylene, pentamethylene, and hexamethylene groups, and the like.Also, as R⁸, there are exemplified methylene, ethylene, propylene,trimethylene, tetramethylene, ethylethylene, pentamethylene, andhexamethylene, polymethylene, phenylene, 1,4-cyclohexylene, and p-xylenegroups, and the like. ##STR6## (in the respective general formulae, R⁶represents a hydrogen atom or a methyl group, R⁷ represents a divalentaliphatic saturated hydrocarbon group having a carbon number of 1-6, R⁸represents a divalent hydrocarbon group having a carbon number of 1-10,and "m" is an integer of 1-10).

The unsaturated compound containing an alicyclic epoxy group representedby the formula (6) to be employed in the present invention is added intoa solution of an alcohol-based, an ester-based, an aromatichydrocarbon-based, and an aliphatic hydrocarbon-based inert organicsolvent containing the unsaturated resin containing acid groups,followed by allowing to react by maintaining both compounds at 20-120°C. for 1-7 hours.

Herein, in the case that the unsaturated aliphatic resin containing acidgroups is an acryl-based resin containing acid groups, it can be allowedto react in reaction conditions of 20-120° C. for approximately 1-5hours.

In a reaction product obtained, the number of unsaturated groups rangesin 0.2-4.0 pieces, preferably 0.7-3.5 pieces of based on 1000 of amolecular weight. In the case of less than 0.2 piece, curability becomesinsufficient in a coating layer, and adhesion and water resistance, andthe like for a substrate become occasionally poor. On the other hand, inthe case that the number of the unsaturated groups is more than 4.0pieces, it is unpreferably anxious that viscosity increases and gelationis caused during the addition reaction with the acryl-based resincontaining acid groups and during a storage of the composition for along time of period. Also, in the reaction product obtained, a numberaverage molecular weight preferably ranges in 1,000-100,000, and morepreferably 3,000-70,000. In the case of less than 1,000, waterresistance becomes poor in a cured layer and, in the case that themolecular weight is more than 100,000, viscosity increases and handlingbecomes inconvenient, unpreferably resulting in that coatability alsobecomes worse and there becomes poor adhesion to a water-resistiblesubstrate. And also, in the reaction product obtained, an acid value ispreferably not more than 300 KOHmg/g. In the case that the acid value ismore than 300 KOHmg/g, unpreferably, water resistance becomesoccasionally poor in the layer.

AN ACTIVE ENERGY RAY-CURABLE TYPE UNSATURATED RESIN COMPOSITION

By mixing a diluent in the above-mentioned reaction product to beemployed in the present invention, there can be obtained an activeenergy ray-curable type unsaturated resin composition according to usesand properties of a coating layer to be required. As the diluent to bemixed in the composition of the present invention, there can be employedan organic solvent and a polymerizable compound. The organic solvent isnot limited in the kind, and there is preferred a solvent having aboiling point higher than the reaction temperature, and further, whichcan dissolve raw materials and the product. For example, there can beexemplified alcohols such as ethyl alcohol, propyl alcohol, isopropylalcohol, and butanol, glycols such as ethylene glycol, propylene glycol,and dipropylene glycol, glycol ethers such as methylcellosolve,propylene glycol monomethylether, and dipropylene glycolmonomethylether, glycol esters such as ethylene glycol diacetate anddipropylene glycol monomethylether acetate, and a mixed solutionthereof. The organic solvent is not particularly limited in the amountto be employed. It can be appropriately selected by a coating method,and it can be diluted as having a viscosity according to respectivecoating methods.

In the case that a dipcoater, and the like are employed, theconcentration of solid content in resins is preferably 1-40% by weightand, in the case that a roll coater and a curtain coater are employed,it is preferably 20-60% by weight or so.

As the polymerizable compound, there can be likewise employed thecompounds exemplified as "a polymer or an oligomer for dilution" in thefirst aspect of the present invention and, further, there can beexemplified a polyolefin-based compound and a polymerizable prepolymer,and the like. Herein, as the polyolefin-based compound, analkali-soluble resin is preferred.

For example, there can be exemplified a PVA, an acrylic resin containingacid groups, and polyolefines containing phenol groups, and the like.Further, as the polymerizable polymer, there can be exemplified, forexample, a resin containing polymerizable unsaturated groups which canbe modified to a water-soluble resin, for example, a resin in which ahydroxyalkyl(meth)acrylate is introduced into a polyol having carboxylicgroups through a polyisocyanate compound, a resin containingpolymerizable unsaturated groups, for example, a (meth)acrylate of apolyester polyol, a (meth)acrylate of a polyether polyol, a(meth)acrylate of an acryl polyol, an adduct of a polyepoxide to(meth)acrylic acid, and a resin in which a hydroxyalkyl(meth)acrylate isintroduced into a polyol through a polyisocyanate compound, and thelike. As other diluents, there can be exemplified an adduct of a monomercontaining hydroxyl group to a monoisocyanate such as butyl isocyanateand phenylisocyanate, a monomer containing adilidine group, and a vinylmonomer containing phosphorus, and the like.

The polymerizable compound is preferably mixed in a range of less than100 parts by weight, more preferably not more than 50 parts by weightbased on 100 parts by weight of resinous solid components in the activeenergy ray-curable type resin composition. Because, hardness, solventresistance, and alkali resistance, and the like are occasionally poor ina resin coating layer.

In the active energy ray-curable type resin composition of the presentinvention, there can be employed together a synergetic agent in order toaccelerate conversion of absorbed photo-energy to polymerization radicalgroups, for example, such as the ring-opening addition catalysts for anepoxide exemplified in the first aspect of the invention. Those may beemployed solely, or in combination of two or more kinds. The catalystsare preferably employed in 0.01-20% by weight, more preferably 0.1-10%by weight based on the compound of the formula (6) or a (co)polymerthereof. In the case of less than 0.01% by weight, an effect as acatalyst is low and, in the case of adding an amount exceeding 20% byweight, curability becomes poor. It is to be noted that aphoto-polymerization initiator may be not added in the case that thecomposition of the present invention is cured by irradiation of anelectronic beam.

As other agents for mixing, there can be added a photo-polymerizationinitiator. As the photo-polymerization initiator, there can be likewiseemployed the photo-polymerization initiator exemplified in the firstaspect of the invention. Those may be employed solely, or in combinationof two or more kinds. Further, the photo-polymerization initiator ispreferably mixed in a range of 0.1-10% by weight based on the activeenergy ray-curable type resin composition. Still further, in thecomposition of the present invention, there can be optionally mixedpigments and dyes, and the like within an extent in which curability byan active energy ray is not deteriorated.

USES

The active energy ray-curable type resin composition of the presentinvention is particularly useful for coatings, printing inks,photo-resists, solder-resists, printing materials, adhesives, andpressure-sensitive adhesives, and the like. In the composition of thepresent invention, a coating layer can be formed by a method in whichcoating is conducted on wooden materials, papers, inorganic materials,plastics, and metals (zinc, iron, copper, and aluminum, and the like)with a coating machine such as, for example, a natural roll coater, areverse roll coater, a gravure roll coater, a screen printer, a curtaincoater, a dip coater, an air spray, an airless spray, a bar-coater, aknife coater, a spin coater, and a brush and dipping coating machine,and the like, followed by curing the coating layer through irradiatingthe active energy ray such as an electronic beam or ultraviolet ray.Thickness in the above-described coating layer is preferably not morethan 2000 μm after dried, and particularly 0.1-1000 μm. In the case thatthe thickness in the coating layer exceeds 2000 μm, curability becomesunpreferably poor at an inside of the coating layer.

Further, as the electronic beam accelerator in order to discharge theactive energy ray, there can be employed a Cockcroft type, a CockcroftWalton type, a Vin de Graph type, a co-transformer type, a transformertype, an insulating core transformer type, a Dynamitron type, a linearfilament type, a broad beam type, an area beam type, a cathode electrodetype, and a high frequency type one, and the like. Herein, although anirradiation amount of the electronic beam, if there is given a necessarydose by which a coating layer is cured, is not particularly limited,there is irradiated a dose of approximately 0.5-20 mega-rad (Mrad) atapproximately 100-2000 keV. Irradiation of the electronic beam ispreferably conducted in an atmosphere of an inert gas. Still further, asirradiating means of the ultraviolet ray in order to discharge theactive energy ray, there can be exemplified a mercury lamp, a highpressure mercury lamp, a xenon lamp, a carbon arc lamp, a metal halidelamp, and sun light, and the like. Irradiation of the ultraviolet ray ispreferably conducted in an atmosphere of air or an inert gas. In thecase that irradiation is conducted in an atmosphere of air,particularly, the high pressure mercury lamp is preferably employed asan irradiating source. In addition, although the irradiation conditionsare different according to an amount absorbed into thephoto-polymerization initiator, irradiation is conducted within severalminutes, usually within a range of 1 second-20 minutes with a beamhaving 3000-4500 Å.

EXAMPLES OF SECOND ASPECT OF INVENTION

Hereinafter, although the present invention is specifically illustratedby Examples, the present invention is not limited by those. It is to benoted that "part" represents "part by weight" except particularlyshowing.

Synthesis Example 1

Into a separable flask equipped with an agitator, a thermometer, aregulator for reflux, a dropwise funnel, and a tube for supplyingnitrogen, there were charged 55 parts of propyleneglycol monomethylether("MMPG" manufactured by Daicel Chemical, Ltd.), 3.3 parts oft-butylperoxy-2-ethylhexanoate ("Perbutyl O" manufactured by NihonYushi, Ltd.), followed by adding dropwise 18 parts of acrylic acid, 30parts of styrene, 35 parts of butylacrylate, 3 parts of2,2-azobis(2-methylbutylonitrile) ("ABN-E" manufactured by NihonHydrazine Kogyo, Ltd.), and 8 parts of "MMPG" over 3 hours after heatinga temperature to 95° C. After the dropwise addition, aging was conductedfor 4 hours to prepare a main polymer having carboxylic groups.

Subsequently, there were added 42 parts of a compound (A) describedhereinafter, 4 parts of triphenylphosphine, and 0.2 part ofmethylhydroquinone into the main polymer solution, followed by allowingto react at 100° C. for 10 hours. Reaction was conducted in anatmosphere of a mixed gas composed of air/nitrogen. By the reaction,there was obtained a resinous solution having an acid value of 20KOHmg/g, a double bond equivalent (g weight of a resin per 1 mol ofunsaturated groups) of 590, and a weight average molecular weight of20,000.

Synthesis Example 2

The same operations were followed as in the Synthesis Example 1, exceptthat a compound (B) described hereinafter was employed in place of thecompound (A) in the Synthesis Example 1. By the operations, there wasobtained a resinous solution having an acid value of 1 KOHmg/g, a doublebond equivalent (g weight of a resin per 1 mol of unsaturated groups) of590, and a weight average molecular weight of 20,000.

Synthesis Example 3

Into a separable flask equipped with an agitator, a thermometer, aregulator for reflux, a dropwise funnel, and a tube for supplyingnitrogen, there were charged 90 parts of butyl alcohol and 4 parts of"Perbutyl O", followed by adding dropwise 23.4 parts of acrylic acid, 40parts of butylmethacrylate, 35 parts of butylacrylate, 3.5 parts of"ABN-E", and 8 parts of methylisobutyl ketone over 3 hours after heatinga temperature to 95° C. After the dropwise addition, aging was conductedfor 4 hours to prepare a main polymer having carboxylic groups.

Subsequently, there were added 64 parts of the compound (A), 10 parts oftriphenylphosphine, and 0.26 part of methylhydroquinone into thesolution, followed by allowing to react at 100° C. for 10 hours.Reaction was conducted in an atmosphere of a mixed gas composed ofair/nitrogen. By the reaction, there was obtained a resin solutionhaving an acid value of 0 KOHmg/g, a double bond equivalent (g weight ofa resin per 1 mol of unsaturated groups) of 500, and a weight averagemolecular weight of 17,000.

Synthesis Example 4

Into a separable flask equipped with an agitator, a thermometer, aregulator for reflux, a dropwise funnel, and a tube for supplyingnitrogen, there were charged 90 parts of butyl alcohol and 4 parts oft-butylperoxy-2-ethylhexanoate (Perbutyl O manufactured by Nihon Yushi,Ltd.), followed by adding dropwise 23.4 parts of acrylic acid, 40 partsof butylmethacrylate, 35 parts of butylacrylate, 3.5 parts of "ABN-E",and 8 parts of methylisobutyl ketone over 3 hours after heating atemperature to 95° C. After the dropwise addition, aging was conductedfor 4 hours to prepare a main polymer having carboxylic groups.

Subsequently, there were added 32 parts of the compound (A), 32 parts ofa compound (C) ("CYM M100" manufactured by Daicel Chemical, Ltd.)described hereinafter, 10 parts of triphenylphosphine, and 0.26 part ofmethylhydroquinone into the solution, followed by allowing to react at100° C. for 10 hours.

Reaction was conducted in an atmosphere of a mixed gas composed ofair/nitrogen. By the reaction, there was obtained a resin solutionhaving an acid value of 0 KOHmg/g, a double bond equivalent (g weight ofa resin per 1 mol of unsaturated groups) of 500, and a weight averagemolecular weight of 17,000.

Synthesis Example 5

Into a separable flask equipped with an agitator, a thermometer, aregulator for reflux, a dropwise funnel, and a tube for supplyingnitrogen, there were charged 100 parts of "MMPG", 4 parts of "PerbutylO", followed by adding dropwise 45 parts of acrylic acid, 20 parts ofmethylmethacrylate, 35 parts of butylacrylate, 3.5 parts of "ABN-E", and10 parts of "MMPG" over 3 hours after heating a temperature to 95° C.After the dropwise addition, aging was conducted for 4 hours to preparea main polymer having carboxylic groups.

Subsequently, there were added 65 parts of the compound (A), 6.5 partsof triphenylphosphine, and 0.27 part of methylhydroquinone into thesolution, followed by allowing to react at 100° C. for 10 hours.Reaction was conducted in an atmosphere of a mixed gas composed ofair/nitrogen. By the reaction, there was obtained a resin solutionhaving an acid value of 100 KOHmg/g, a double bond equivalent (g weightof a resin per 1 mol of unsaturated groups) of 500, and a weight averagemolecular weight of 17,000.

Synthesis Example 6

Into a separable flask equipped with an agitator, a thermometer, aregulator for reflux, a dropwise funnel, and a tube for supplyingnitrogen, there were charged 100 parts of "MMPG" and 4 parts of"Perbutyl O", followed by adding dropwise 45 parts of acrylic acid, 20parts of methylmethacrylate, 35 parts of butylacrylate, 3.5 parts of"ABN-E", and 10 parts of "MMPG" over 3 hours after heating a temperatureto 95° C. After the dropwise addition, aging was conducted for 4 hoursto prepare a main polymer having carboxylic groups.

Subsequently, there were added 33 parts of the compound (A), 32 parts ofthe compound (C), 6.5 parts of triphenylphosphine, and 0.27 part ofmethylhydroquinone into the solution, followed by allowing to react at100° C. for 10 hours. Reaction was conducted in an atmosphere of a mixedgas composed of air/nitrogen. By the reaction, there was obtained aresin solution having an acid value of 100 KOHmg/g, a double bondequivalent (g weight of a resin per 1 mol of unsaturated groups) of 500,and a weight average molecular weight of 17,000.

Synthesis Example 7

Into a separable flask equipped with an agitator, a thermometer, aregulator for reflux, a dropwise funnel, and a tube for supplyingnitrogen, there were charged 55 parts of "MMPG", 3.3 parts of "PerbutylO", followed by adding dropwise 18 parts of acrylic acid, 30 parts ofstyrene, 35 parts of butylacrylate, 3 parts of "ABN-E", and 8 parts of"MMPG" over 3 hours after heating a temperature to 95° C. After thedropwise addition, aging was conducted for 4 hours to prepare a mainpolymer having carboxylic groups. Subsequently, there were added 30parts of glycidylmethacrylate, 3 parts of triphenylphosphine, and 0.2part of methylhydroquinone into the solution, followed by allowing toreact at 100° C. for 10 hours. Reaction was conducted in an atmosphereof a mixed gas composed of air/nitrogen. By the reaction, there wasobtained a resin solution having an acid value of 20 KoHmg/g, a doublebond equivalent (g weight of a resin per 1 mol of unsaturated groups) of530, and a weight average molecular weight of 18,000. ##STR7##

Example 1

10 parts by weight of α-hydroxyisobutylphenone was added into 300 partsby weight of the solution in the Synthesis Example 1 to prepare asolution, and the solution was coated on an aluminum plate with abar-coater, followed by allowing to cure through irradiation of a UV for5 seconds with a high pressure mercury lamp of 120 W/cm after drying at80° C. for 15 minutes.

Thickness of coating layer was approximately 20 μm. Also, there weremeasured adhesion and water resistance in the coating layer. Results areshown in Table 2.

Example 2

There were added 100 parts by weight of a compound (D) described belowwhich is a vinyl monomer ("Aronix M5700" manufactured by Toa-Gosei,Ltd.) and 20 parts by weight of tripropyleneglycol diacrylate into 300parts by weight of the solution in the Synthesis Example 1 to prepare asolution, followed by removing MMPG in the solution by reducing pressurewhile supplying air after heating to 100° C. Further, there was added 10parts by weight of α-hydroxyisobutylphenone. Composition was coated onan aluminum plate with a bar-coater, followed by allowing to curethrough irradiation with a high pressure mercury lamp of 120 W/cm for 5seconds. Thickness of coating layer was 20 μm. There were measuredadhesion and water resistance in the coating layer. ##STR8##

Example 3

There were added 106 parts by weight of "Aronix M5700" and 22 parts byweight of tripropyleneglycol diacrylate into 312 parts by weight of thesolution in the Synthesis Example 2.

Solvent was likewise removed as in the Example 2, and there was added 17parts by weight of α-hydroxyisobutylphenone.

Further, curing was conducted by the same methods as in the Example 2.

Example 4

There was added 6 parts by weight of α-hydroxyisobutyl phenone into 220parts by weight of the solution in the Synthesis Example 3 to prepare asolution. The solution was coated on an aluminum plate with abar-coater, followed by allowing to cure through irradiation of a UV for2 seconds with a high pressure mercury lamp of 120 W/cm after drying at80° C. for 15 minutes.

Thickness of coating layer was approximately 20 μm. There were measuredadhesion and water resistance in the coating layer.

Example 5

There were added 50 parts by weight of "Aronix M5700" and 12 parts byweight of tripropyleneglycol diacrylate into 220 parts by weight of thesolution in the Synthesis Example 4, followed by removing n-butanol andmethylisobutyl ketone in the solution at reducing pressure whilesupplying air after heating to 100° C. Further, there was added 10 partsby weight of α-hydroxyisobutylphenone. Composition was coated on analuminum plate with a bar-coater, followed by allowing to cure throughirradiation for 2 seconds with a high pressure mercury lamp of 12 W/cm.Thickness of coating layer was 20 μm. There were measured adhesion andwater resistance in the coating layer.

Comparative Example 1

After there was added 8 parts by weight of α-hydroxy isobutylphenoneinto 260 parts by weight of the solution in the Synthesis Example 7, thesame test was conducted as in the Example 1.

Comparative Example 2

After there were added 80 parts by weight of "Aronix M5700" and 15 partsby weight of tripropyleneglycol diacrylate into 250 parts by weight ofthe solution in the Synthesis Example 7, and solvent was likewiseremoved as in the Example 2, there was added 13 parts by weight ofα-hydroxyisobutylphenone. Further, curing was conducted by the samemethods as in the Example 2.

                                      TABLE 2                                     __________________________________________________________________________                                  Comparative                                       Example Example                                                             1         2    3    4    5    1    2                                          __________________________________________________________________________    Curability                                                                         Excellent                                                                          Excellent                                                                          Excellent                                                                          Excellent                                                                          Excellent                                                                          Excellent                                                                          Excellent                                    Adhesion 100/100 100/100 100/100 100/100 100/100 70/100 80/100                Water 100/100 100/100 100/100 100/100 100/100 20/100 50/100                   resistance                                                                  __________________________________________________________________________

Example 6

There were added 50 parts by weight of tripropyleneglycol diacrylate, 50parts by weight of 1,6-hexanediol diacrylate, and 50 parts by weight oftrimethylolpropane triacrylate into 264 parts by weight of the solutionin the Synthesis Example 3, followed by removing n-butanol which is asolvent in the solution at reducing pressure while supplying air afterheating to 100° C.

Further, there was added 62 parts by weight of a Titanium White,followed by dispersing with a ball-mill to prepare a white-coloredcoating. The coating was coated on a plaster board having the thicknessof 1.5 cm with a curtain-coater, followed by allowing to cure thecoating layer through irradiation of an electronic beam of 7 mega-rad toprepare a plaster tile.

Thickness of the coating layer is approximately 100 μm.

Adhesive property to the plaster was excellent, and as a result ofevaluation of outer appearance and adhesive property by sticking to awall for 3 months, it was excellent without changing from an initialstate.

Example 7

There were kneaded 198 parts by weight of the solution in the SynthesisExample 5, 20 parts by weight of a phenol novolak epoxy resin (an epoxyequivalent of 173), 5 parts by weight of α-hydroxyisobutylphenone, and0.5 parts by weight of Phthalocyanin Green with a three-roll.Composition was employed as a solder resist ink for a printed circuitboard. Subsequently, the ink was coated on a copper-through-hole printedcircuit board by a screen-printing method. After drying (layer thicknessof 15-20μ) at 70° C. for 10 minutes, a film on which a pattern is formedwas closely attached to the board, followed by irradiating the dose of1000 mJ/cm² with an ultra high pressure mercury lamp of 3 kw. Further,unexposed portions were removed with 1%-solution of sodium carbonate,followed by heating at 140° C. for 30 minutes to prepare a solder resistlayer. The resist layer was excellent in heat resistance such as solderresistance, and chemical resistance to acids and alkalis. Results areshown in Table 3.

                  TABLE 3                                                         ______________________________________                                                       Example                                                                       7      8                                                       ______________________________________                                        Solder resistance                                                                              Excellent                                                                              Excellent                                             Acid resistance 100/100 100/100                                               Acid resistance 100/100 100/100                                             ______________________________________                                    

Example 8

As a result that the same tests were conducted as in the Example 7 usingthe solution in the Synthesis Example 6, it was identified that anexcellent resist layer can be formed. The resist layer was likewiseexcellent in heat resistance such as solder resistance, and chemicalresistance to acids and alkalis as in the Example 7.

Measured Item

(1) Curability: Curability was evaluated by a gel fraction. Driedcoating layer was stripped from a base material, and it was extracted byacetone for 6 hours at a reflux temperature with a Soxhlet Extractor.Residual components from the coating layer were measured, and 90% andmore was regarded excellent.

(2) Adhesion: 100 pieces of cross-hatched cuts were formed on a testpiece with a interval of 1 mm according to JIS D-0202 Testing method,and those were peeled by a cellophane-made pressure sensitive tape. Thenumber of the cross-hatched cuts which are not peeled off is shown as anumerator, and original number (100 pieces) of the cross-hatched cuts isshown as a denominator.

(3) Water resistance: Adhesion after immersion was measured to show aswater resistance. Measurement was conducted as follows.

A coated plate was immersed in warm water of 50° C. for 1 day, and waterwas wiped from the coated plate. Further, after leaving as it is for 1hour, the same test was conducted as in adhesion.

(4) Solder resistance: It was decided as 1 cycle that a test piece isfloated on a solder bath of 260° C. for 10 seconds according to JISC6481 Testing method, and 3 cycles were conducted to visually evaluate.

(5) Acid resistance: After immersed in 20%-hydrochloric acid at 30° C.for 1 hour, evaluation was conducted by a cross-hatched test.

(6) Alkali resistance: After immersed in 1%-sodium carbonate aqueoussolution at 30° C. for 1 hour, evaluation was conducted by across-hatched test.

POSSIBILITY OF UTILIZATION IN INDUSTRY BY THE SECOND ASPECT OF THEINVENTION

In the active energy ray-curable type unsaturated resin composition ofthe present invention, there are introduced unsaturated groups which arecurable by an active energy ray into a reaction product obtained by anaddition reaction of an unsaturated compound containing an alicyclicepoxy group to acid groups derived from an unsaturated resin containingacid groups, which readily reacts depending upon a ring-openingpolymerization reaction of epoxy groups. In a coating layer formed fromthe composition, since a chemical bond is a bond having a relativelylarge steric hindrance, which is formed by a chemical reaction of acidgroups in the acrylic resin with the alicyclic epoxy groups, the coatinglayer is chemically stable to a substance which accelerates hydrolysis,for example, water and rain water, and the like. Accordingly, the activeenergy ray-curable type unsaturated resin composition of the presentinvention can provide a coating layer having a remarkable effect, forexample, excellent durability such as water resistance, etc.

TECHNICAL FIELD OF THIRD ASPECT OF THE INVENTION

The third aspect of the invention relates to an active energyray-polymerizable unsaturated resin composition and a liquid-state orpowder-state active energy ray-curable resin composition composed of theresin composition which is excellent in chemical resistance, adhesion,and heat resistance.

BACKGROUND ART OF THIRD ASPECT OF THE INVENTION

Heretofore, as a photo-curable composition, there has been employed acomposition in which inorganic fillers are mixed. The inorganic fillersare usually mixed in a large amount into a base material in order toobtain a photo-cured layer which is excellent in physical propertiessuch as hardness and heat resistance. However, photo-transmittance inthe resin composition lowers by the inorganic fillers mixed, orcurability becomes worse in the layer, and further, the layer becomesbrittle and porous, resulting in that there occasionally deterioratemechanical properties, water resistance, adhesion, and chemicalresistance, and the like in the layer. Further, a powder-state curableresin composition, in which there can be conducted a handling such ascoating without the use of organic solvents, could be readily employedfrom a viewpoint of environmental protection in recent years.

DISCLOSURE OF THIRD ASPECT OF THE INVENTION

The present inventors, as a result of a repeated intensiveinvestigation, have found that a resin composition can be modified intoa powder-state, which is obtained by a reaction of a specifiedunsaturated compound containing an alicyclic epoxy group with colloidalsilica in the presence of a metal chelate and/or a metal alkoxide, and acurable composition composed of the resin composition is excellent incurability by irradiation of an active energy ray and, further, a curedlayer is excellent in mechanical properties, water resistance, chemicalresistance, and adhesion, and the like, and the present invention wascompleted.

That is, the present invention provides an active energyray-polymerizable unsaturated resin composition obtainable by allowingto react an unsaturated compound (E) containing an alicyclic epoxy grouprepresented by formula (6) with a colloidal silica (F) in the presenceof a metal chelate and/or metal alkoxide (hereinafter, referred to as"metal compound") (G).

Further, there is provided a powder-state active energyray-polymerizable unsaturated resin composition obtained by removing asolvent from the active energy ray-polymerizable unsaturated resincomposition. Still further, there is provided a liquid-state orpowder-state active energy ray-curable composition which comprises theliquid-state or powder-state active energy ray-polymerizable unsaturatedresin composition. Hereinafter, the present invention is illustrated indetail.

    R.sub.2 --O--CO--NH--CH═CH--R.sup.1                    (6)

(in the formula, R¹ represents a hydrogen atom, an aromatic hydrocarbongroup, or a saturated or unsaturated aliphatic hydrocarbon group, R²represents formula (2) or formula (3)), ##STR9## (in the formula, R⁴ andR⁵ represent a hydrogen atom, a methyl group or ethyl group,respectively, "m" is an integer of 4-8, and "n" is an integer of 1-10).

BEST MODE FOR CARRYING OUT THE THIRD ASPECT OF THE INVENTION UNSATURATEDCOMPOUND (E) CONTAINING AN ALICYCLIC EPOXY GROUP

The unsaturated compound (E) containing an alicyclic epoxy group to beemployed in the present invention is a compound having one alicyclicepoxy group and at least one of the active energy ray-polymerizableunsaturated group in the molecule, and it is represented by theabove-described formula (6) and, it is prepared by the same method andit has the same structural formula as in the compound in which R² isrepresented by the formula (2) or (3) in the compound represented by theformula (1) of the first aspect of the present invention. Theunsaturated compound (E) containing an alicyclic epoxy group ischaracterized in that it contains one alicyclic epoxy group alone in themolecule. The reason why it is one depends upon that if it has two ormore alicyclic epoxy groups, viscosity in a system occasionallyincreases and causes gelation in a reaction with the colloidal silica(F) in the presence of the metal compound (G).

The reason why the epoxy group is alicyclic depends upon that since areaction of the epoxy group with a silanol group in the colloidal silica(F) is poor in a compound having an aliphatic epoxy group such asglycidyl group, the colloidal silica component does not sufficientlyconnect to a compound containing an unsaturated group, resulting in thatthere cannot be obtained a cured layer having excellent outer appearanceand properties. Further, a carbon--carbon double bond in the unsaturatedcompound (E) containing an alicyclic epoxy group is an active energyray-polymerizable unsaturated group, and it causes a polymerizationreaction by being activated with an active energy ray such as visiblelight, an ultraviolet ray, and an electronic beam.

COLLOIDAL SILICA (F)

The colloidal silica (F) to be employed in the present invention meansone in which there is dispersed silica powder having average particlesize of 0.001-100 μm in an organic solvent.

As the colloidal silica to be employed in the present invention, thereis preferred one in which there is dispersed silica powder having asilanol group at the surface and having average particle size of0.005-0.1 μm in an organic solvent. By the presence of the silanolgroup, there can be readily conducted a reaction of the silanol group inthe colloidal silica with the aliphatic epoxy group, and a curablecomposition obtained using this one is excellent also in curability byirradiation of an active energy ray, mechanical properties of a layer,water resistance, chemical resistance, and adhesion, etc. In the casethat the average particle size is larger than 0.1 μm, a cured articleoccasionally causes whitening, and sedimentation stability occasionallylowers. On the other hand, in the case that the average particle size issmaller than 0.005 μm, viscosity increases in a composition obtained,unpreferably resulting in that handling becomes difficult.

As the organic solvent to be employed for the colloidal silica (F), ifit can stably disperse the silica, it is can be employed without beingparticularly limited. There can be exemplified monovalent alcoholshaving a carbon number of 1-6 such as methyl alcohol, ethyl alcohol,n-propyl alcohol, iso-propyl alcohol, n-butyl alcohol, iso-butylalcohol, sec-butyl alcohol, tert-butyl alcohol, n-pentyl alcohol, andn-heptyl alcohol, polyvalent alcohols such as ethylene glycol,diethylene glycol, propylene glycol, and dipropylene glycol, ethers suchas ethyl cellosolve, butyl cellosolve, propylene glycol monomethylether,diethylene glycol monomethylether, ethylene glycol dimethylether, anddiethylene glycol dimethylether, amides such as N,N-dimethylformamide,and nitriles such as acetonitrile, and the like. Further, organicsolvents other than the above-described ones, for example, aromatichydrocarbons, esters, and ketones, and the like, can be employed incombination.

METAL COMPOUND (G)

As the metal compound (G) to be employed in the present invention, thereare metal chelates and metal alkoxides. As the metal chelates, there canbe exemplified an aluminum chelate compound, a titanium chelatecompound, or a zirconium chelate compound, and there can be alsoemployed compounds described in JP-A-01129060 Official Gazette.Specifically, there can be exemplified diisopropoxyethyl acetoacetatealuminum, tris(ethylacetoacetate)aluminum,isopropoxy-bis(ethylacetoacetate)aluminum,monoacetylacetonate-bis(ethylacetoacetate)aluminum,tris(n-propylacetoacetate)aluminum, tris(isopropylacetoacetate)aluminum,tris(n-butylacetoacetate)aluminum,monoethylacetoacetate-bis(acetylacetonate)aluminum,tris(acetylacetonate)aluminum, tris(propionylacetonate)aluminum,acetylacetonate-bis(propionylacetonate)aluminum,diisopropoxy-bis(ethylacetoacetate)titanium,diisopropoxy-bis(acetylacetonate)titanium,tetrakis(n-propylacetoacetate)zirconium,tetrakis(acetylacetonate)zirconium, andtetrakis(ethylacetoacetate)zirconium, and the like. In the presentinvention, these may be employed solely or in combination.

As the metal alkoxides, there can be employed a compound in which analkoxy group, preferably, an alkoxy group having a carbon number of 1-15connects to metals such as aluminum, titanium, zirconium, sodium,potassium, calcium, and lithium.

The compounds may be associated. Specifically, there are preferablyexemplified aluminum triisopropoxide, aluminum tri-sec-butoxide,aluminum tri-n-butoxide, titanium tetraisopropoxide, titaniumtetra-n-butoxide, titanium tetraisobutoxide, titanium tetra-t-butoxide,zirconium tetraisopropoxide, zirconium tetra-n-propoxide, zirconiumtetra-n-propoxide, zirconium tetraisobutoxide, zirconiumtetra-n-butoxide, and zirconium tetra-t-butoxide, and the like. In thepresent invention, these may be employed solely or in combination of twoor more kinds.

ACTIVE ENERGY RAY-POLYMERIZABLE UNSATURATED RESIN COMPOSITION

The active energy ray-polymerizable unsaturated resin composition of thepresent invention (hereinafter, referred to as "unsaturated resincomposition") can be prepared by allowing to react the above-describedunsaturated compound (E) containing an alicyclic epoxy group with thecolloidal silica (F) in the presence of a metal compound (G).

The unsaturated compound (E) containing an alicyclic epoxy group can bemixed with the colloidal silica (F) in an appropriate ratio according toproperties of coating layers to be required. There are usually mixed20-80% by weight, preferably 20-70% by weight of the compound (E) and80-20% by weight, preferably 80-30% by weight of the colloidal silica(F) based on the total amount of both solid components. In the case thatthe colloidal silica (F) is less than 20% by weight, properties such ashardness and heat resistance are not sufficient in a coating layer. Onthe other hand, in the case that the colloidal silica (F) exceeds 80% byweight, unpreferably, cracks are caused in a coating layer, andtransparency become occasionally poor.

Further, "any one of other alicyclic epoxy compounds containing anunsaturated group" employed in the second aspect of the invention can beemployed within a range of 99/1-1/99 parts by weight based on thecompound (E).

The metal compound (G) is preferably mixed in a proportion of 0.01-10parts by weight, particularly, 0.1-5 parts by weight based on 100 partsby weight of the total solid amount of the compound (E) and thecolloidal silica (F). In the case of less than 0.01 part by weight,there is readily caused inferiority in curing, and in the case ofexceeding 5 parts by weight, storage stability becomes poor, andphysical properties in the coating layer are occasionally adverselyaffected.

The "unsaturated resin composition" of the present invention can beobtained by heating the compound (E) and the colloidal silica (F) atreaction temperature of 40-130° C. for 1-10 hours under the presence ofthe metal compound (G).

POWDER-STATE ACTIVE ENERGY RAY-POLYMERIZABLE UNSATURATED RESINCOMPOSITION

The powder-state active energy ray-polymerizable unsaturated resincomposition of the present invention can be prepared by removingsolvents from the above-described "unsaturated resin composition"according to a conventional method. Further, the powder-state activeenergy ray-curable resin composition (hereinafter, referred to as"curable composition") of the present invention is a composition inwhich curable resins and curable monomers shown below are mixed into theabove-described "unsaturated resin composition". It is to be noted thatin the "curable composition", the component of the colloidal silica (F)is preferably mixed as adjusted to a proportion of 20-80% by weight,preferably 30-80% by weight based on the total solid components in the"curable composition".

As a curable resin to be mixed, there can be employed conventionallyknown ones by appropriately selecting.

Specifically, there can be preferably employed oligomers such as anepoxy acryl-based oligomer, a polyester-based oligomer, a urethaneacryl-based oligomer, an acryl-based oligomer, an oligoester acryl-basedoligomer, an ether acryl-based oligomer, a butadiene-based oligomer, andan acryl-based oligomer containing a spirane ring. In the presentinvention, these preferably have at least one of an active energyray-polymerizable unsaturated group on average, and a molecular weightis preferably 100-20,000.

Further, as a curable monomer to be mixed, there can be employedconventionally known ones by appropriately selecting.

Specifically, there can be exemplified a monofunctional vinyl monomersuch as, for example, a methyl(meth)acrylate, an ethyl(meth)acrylate, abutyl(meth)acrylate, 2-ethylhexylacrylate, a2-hydroxypropyl(meth)acrylate, a glycidyl(meth)acrylate, a (meth)acrylicacid, a (meth)acrylic amide, and styrene, a di- or tri-ester compound ofa polyvalent alcohol such as ethyleneglycol, trimethylolpropane,glycerine, and pentaerythritol with a (meth)acrylic acid.

In the case that the "unsaturated resin composition" has a silanolgroup, curability in a resin and monomer to be mixed is improved bymixing compounds containing a functional group capable of reacting withthe silanol group. As the compounds containing the functional groupcapable of reacting with the silanol group, there are compounds having(i) epoxy group, (ii) silanol group, (iii) hydrolyzable group whichdirectly connects to silicone, (iv) hydroxyl group, and (v) isocyanategroup, and the like. By mixing such the compounds, since theresimultaneously occur a curing reaction by irradiation of an activeenergy ray and a curing reaction by heating, there is an effect thatthere are improved properties, etc. in a coating layer.

As the compounds having epoxy group (i), there can be exemplified ahomopolymer of the above-described compound (E), a copolymer of thecompound (E) with the above-described monomers except a (meth)acrylicacid, an alicyclic compound such as an alicyclic epoxy resin ("Chissonox201" and "Chissonox 206" which are a product manufactured by Chisso,Ltd.), and further, the compounds described below. It is to be notedthat although there can be also employed a compound having analiphatic-type epoxy group, it is occasionally inferior in reactivitycompared to the compound having an alicyclic epoxy group. ##STR10##

As the compounds having silanol group (ii) or the hydrolyzable group(iii) which directly connects to silicone, for example, an alkoxy group,an aryloxy group, and an acyloxy group, and the like, which have asilanol group and/or an alkoxysilane group, there can be preferablyemployed, for example, a polysiloxane-based monomer described inJP-A-62197423 Official Gazette, a monomer such as a vinyl monomer havingan alkoxysilane group described in JP-A-63108049 Official Gazette, or apolymer containing the monomer as an essential component.

As the compounds having hydroxyl group (iv), there can be preferablyemployed, for example, a polyester-based polyol, a polyether-basedpolyol, an acryl-based polyol, a polysiloxane-based polyol, apolyurethane-based polyol, and a modified polyol therefrom. As thecompounds having isocyanate group (v), there can be preferably employed,for example, a product in which polyisocyanates, for example, isophoronediisocyanate, and the like are allowed to react with the above-describedpolyols.

In the "curable composition" of the present invention, there can beoptionally mixed organic solvents, for example, aromatic hydrocarbons,alcohols, ethers, esters, and ketones. By mixing the organic solvents,there can be adjusted viscosity, the thickness of a layer, stability,and fluidity, etc., resulting in becoming readily employed. Further, thewater-soluble "curable composition" can be also obtained using the"unsaturated resin composition". Specifically, a resin capable ofbecoming water soluble is selected from the above-described resins. Asthe resin capable of becoming water soluble, there can be employed aconventionally known resin, specifically, unsaturated resins having acationic or anionic group described in JP-B-77021526, JP-A-62262855,JP-A-64004671, and JP-A-64004672 Official Gazettes, more specifically, aresin in which a resin containing acid groups is neutralized by anamine, and a resin in which a resin containing acid groups isquartenerized by a compound having glycidyl group, a resin in which acidgroups are neutralized by an alkali, a resin in which a compound havingan unsaturated group and epoxy group is partially added to a resincontaining acid groups, and then residual acid groups are neutralized byan amine, a resin quartenerized by a compound having glycidyl group, aresin in which a hydrophilic group is introduced using isocyanate group,and a resin having hydroxyl group and a polyether group, and the like.Still further, in the case that the "unsaturated resin composition" hassilanol groups, there is selected a water-soluble compound from theabove-described compounds containing a functional group capable ofreacting with the silanol group. Specifically, there can be exemplifieda silane compound containing mercaptan group, a silane compoundcontaining amino group, and a silane compound containing hydroxyl group.

POWDER-STATE ACTIVE ENERGY RAY-CURABLE UNSATURATED RESIN COMPOSITION

In order to obtain the powder "curable composition" from the"unsaturated resin composition", there is selectively mixed a resincapable of being powdered from the above-described resins. In the casethat the "unsaturated resin composition" has the silanol group, acompound which can be powdered is selected from the above-mentionedcompounds containing a functional group capable of reacting with thesilanol group.

In the "curable the composition" of the present invention, there can beoptionally mixed coloring agents, dispersants, and agents forcontrolling fluidity, and the like. Also, the liquid-state orpowder-state "curable composition" can be cured by irradiation of anactive energy ray such as an electronic beam, an ultraviolet ray, andvisible light. In the case that it is cured by irradiation of theultraviolet ray or visible light, there can be mixedphoto-polymerization initiators, sensitivity accelerators, and coloringagents into the composition.

As the photo-polymerization initiators, there can be employed thephoto-polymerization initiators exemplified in the first aspect of theinvention. These may be employed solely or in combination of two or morekinds. Further, the photo-polymerization initiators are preferably mixedin a range of 0.01-10% by weight based on the "curable composition".

A synergetic agent for accelerating a conversion of photo-energyabsorbed to a free radical for initiation of polymerization can be mixedwith the liquid-state or powder-state "curable composition" of thepresent invention, for example, a catalyst for addition by ring-openingof an epoxide can be employed together. As the catalyst for addition byring-opening of an epoxide to be mixed, there can be employed thecatalysts for addition by ring-opening of an epoxide exemplified in thefirst aspect of the invention. These may be employed solely or incombination of two or more kinds. These catalysts are preferablyemployed in a range of 0.01-10% by weight, preferably 0.1-5% by weightbased on the "curable composition".

In the case of less than 0.01% by weight, a reaction rate of additionitself becomes slow, resulting in that it is practically unpreferredand, in the case of exceeding 10% by weight, physical properties areadversely affected in a coating layer. It is to be noted that in thecase of curing the compound of the present invention and the compositionthereof by irradiation of an electronic beam, the photo-polymerizationinitiator may also be not mixed.

As the coloring agents to be mixed into the liquid-state or powder-state"curable composition" of the present invention, there can be employedxanthone eocine and ketocoumarins, and the like. These may be employedsolely or in combination of two or more kinds. These catalysts arepreferably employed in a range of 0.01-70% by weight, preferably 0.1-50%by weight based on the "curable composition". In the case of less than0.01% by weight, a reaction rate of addition itself becomes slow,resulting in that it is practically unpreferred and, in the case ofexceeding 70% by weight, physical properties are adversely affected in acoating layer.

USES

The liquid-state or powder-state "curable composition" of the presentinvention can be applied for base materials such as woods, papers,inorganic materials, plastics, and metals.

Particularly, it is useful for coatings, printing inks, encapsulants,photo-resists, solder resists, plating resists, materials for printingnegatives, and adhesives, and the like.

Of those, it is desirably employed as, particularly, encapsulants,protecting layers for electronic parts, and a variety of resist layersbecause of excellent chemical resistance, adhesion, and heat resistance.It depends upon that the liquid-state or powder-state "curablecomposition" of the present invention has high hardness and excellentchemical resistance in a coating layer. It is to be noted that if awater-based product from the "curable composition" is employed, it canbe employed for a copper foil-laminated insulation board for a printedcircuit as a negative type or positive type anionic electro-depositioncoating, or a negative type or positive type cationic electro-depositioncoating.

There can be employed a method for forming a coating layer using the"curable composition" of the present invention, thickness of the coatinglayer, an electronic beam accelerator for discharging the active energyray, irradiation amount of the active energy ray, an irradiation sourceof an ultraviolet ray for discharging the active energy ray, andirradiation conditions, and the like in the same conditions as describedin the second aspect of the invention.

EXAMPLES OF THIRD ASPECT OF THE INVENTION

Hereinafter, although the present invention is specifically illustratedby Examples, the present invention is not limited by those. It is to benoted that "part" and "%" represent "part by weight" and "%" by weight,except particularly showing.

Synthesis Example 1

Into a separable flask equipped with an agitator, a thermometer, aregulator for reflux, a dropwise funnel, and a tube for supplyingnitrogen, there were charged 1000 parts of a silica sol ("IPA-ST"manufactured by Nissan Kagaku Kogyo, Ltd., which has solid content of30% and average particle size of 0.01-0.02 μm), 150 parts of a compound(A) described hereinafter, 0.5 part of methylmethacrylatetris(acetylacetonate), and 0.04 part of aluminum methoxyhydroquinone,followed by allowing to react while agitating for 6 hours at 110° C. toobtain a resin solution having solid content of 39%.

Synthesis Example 2

The same operations were followed as in the Synthesis Example 1, exceptthat 100 parts of the compound (A) and 50 parts of a compound (B)described hereinafter were employed in place of 150 parts of thecompound (A) to obtain a resin solution.

Solid content was 39% in the resin solution obtained.

Synthesis Example 3

The same operations were followed as in the Synthesis Example 1, exceptthat glycidylmethacrylate was employed in place of the compound (A) toobtain a resin solution. Solid content was 39% in the resin solutionobtained.

Synthesis Example 4

The resin solution obtained in the Synthesis Example 1 was dried at 40°C. and reduced pressure to obtain a resin powder.

Synthesis Example 5

The resin solution obtained in the Synthesis Example 3 was dried at 40°C. and reduced pressure to obtain a resin powder.

Example 1

There were mixed 1150 parts of the resin solution obtained in theSynthesis Example 1 and 15 parts of α-hydroxyisobutyl phenone, followedby spray-coating onto the surface of an ABS(acrylonitrile-butadiene-styrene copolymer) plate so that the thicknessof a layer becomes 20 μm in a dry state. After solvent was removed byheating at 70° C. for 10 minutes, exposure was conducted for 30 secondsfrom distance of 30 cm with a high pressure mercury lamp of 5 kw toobtain a layer. The layer was a continuous layer without defects such ascracks. Also, the layer was transparent and, moreover, it showed anexcellent pencil hardness of 7H.

Comparative Example 1

The same operations were followed as in the Example 1, except that theresin solution in the Synthesis Example 3 was employed in place of theresin solution in the Synthesis Example 1 to obtain a layer. The layerdid not form a continuous layer and, as a result of rubbing the surfaceby hand, it changed to a powder state and clung to the hand.

Example 2

There were mixed 1050 parts of the resin solution in the SynthesisExample 2, 150 parts of trimethylolpropane triacrylate, and 20 parts ofbenzoin ethylether, followed by spray-coating onto the surface of a zincphosphate-treated steel plate so that the thickness of a layer becomes30 μm in a dry state. After solvent was removed by heating at 70° C. for10 minutes, exposure was conducted for 20 seconds from distance of 50 cmwith a high pressure mercury lamp of 5 kw to obtain a layer. The layerwas a continuous layer without defects such as cracks. The layer wastransparent and, moreover, it showed pencil hardness of 8H, andcross-hatched adhesion was 100/100, which were excellent.

Comparative Example 2

The same operations were followed as in the Example 2, except that 1050parts of the resin solution in the Synthesis Example 3 was employed inplace of 1150 parts of the resin solution in the Synthesis Example 2 toobtain a layer. In the layer, there were caused fine cracks, and it waspoor as a continuous layer. Also, the layer was not transparent and,cross-hatched adhesion was 0/100 and, as a result of pencil hardness, itwas not able to be measured because the layer was stripped by scratchingwith a pencil.

Example 3

There was dispersed in a ball mill for 6 hours a mixture composed of 450part of the resin powder in the Synthesis Example 4, 200 parts of anepoxy acryl oligomer [1 mol of "Epikote 828 (a Bis-A type glycidyletherhaving an epoxy equivalent of 190 which is a liquid-state resin)"manufactured by Shell Kagaku, Ltd. is allowed to react with 2 mol ofacrylic acid], 50 parts of 2-hydroxy-3-benzyloxypropyl acrylate, and 25parts of a compound (C) described hereinafter. The mixture was suppliedinto a mild steel-made square cup having 1 cm², and exposure wasconducted for 40 seconds from distance of 30 cm with a high pressuremercury lamp of 5 kw, followed by heating at 140° C. for 60 minutes toobtain a cast article. A thermocycle test was conducted in relation tothe cast article. As a result, change was nothing before and after thethermocycle test.

Comparative Example 3

The same operations were followed as in the Synthesis Example 4, exceptthat the resin powder in the Synthesis Example 5 was employed in placeof the resin powder in the Synthesis Example 4 to obtain a cast article.A thermocycle test was conducted in relation to the cast article by thesame methods as in the Example 4. As a result, cracks were caused in thecast article at period of 10 cycles.

Example 4

There were added 0.1 part of hydroquinone and 288 parts of acrylic acidinto a resin solution in which 1100 parts of an epoxy resin ("Epikote180S70 which is a cresol novolak epoxy resin having an epoxy equivalentof 210" manufactured by Shell Kagaku, Ltd.) is dissolved into 1045 partsof butyl cellosolve, followed by continuing a reaction while heating to100° C. until an acid value becomes not more than 5. After cooled to 70°C., there were added 122 parts of thiodiglycol acid and 60 parts ofacetic acid, and a reaction was conducted at 70° C. for 8 hours toobtain a resin solution having the solid content of 60% of a resinhaving acryloyl groups and hydroxyl groups. Subsequently, there wascoated a mixture composed of 100 parts of the resin solution, 150 partsof the resin solution in the Synthesis Example 1, 15 parts of thecompound (C), and 5 parts of benzoin ethylether onto a copperfoil-laminated board having through holes so that there is formed adried layer having the thickness of 30 μm. Subsequently, after solventwere removed by heating at 70° C. for 10 minutes, exposure was conductedwith an irradiation dose of 300 mJ/cm² from distance of 50 cm using anultra high pressure mercury lamp of 80 w/cm through a negative mask,followed by removing an unexposed layer by treating with a developer fora fixed period of time. Remained layer was heated at 140° C. for 30minutes to form a resist layer pattern on the copper foil-laminatedboard. Results of properties in the layer obtained are shown in Table 4.

Example 5

Into a 2-liter separable flask equipped with a regulator, a dropwisefunnel, and a tube for supplying nitrogen, there were charged 300 g ofdipropyleneglycol monomethylether ("MFDG" manufactured by NihonNyukazai, Ltd.), 12.0 g of t-butylperoxy-2-ethylhexanoate ("Perbutyl O"manufactured by Nihon Yushi, Ltd.), and after a temperature was elevatedto 95° C., there were added dropwise 172 g of methacrylic acid, 126 g ofmethylmethacrylate, 9.5 g of 2,2-azobis(2-methylbutylonitrile) ("ABN-E"manufactured by Nihon Hydrazine Kogyo, Ltd.), and 200 g of "MFDG" over 3hours. After the dropwise addition, aging was conducted for 4 hours toprepare a main polymer having carboxylic groups. Subsequently, therewere added 202 g of epoxycyclohexyl methylacrylate ("Cyclomer A200"manufactured by Daicel Chemical Industries, Ltd.), 2 g oftriphenylphosphine, and 1.0 g of methylhydroquinone to allow to reactwith the main polymer at 100° C. for 10 hours. Reaction was conducted ina mixed gases atmosphere of air/nitrogen, whereby, there was obtained aresin solution having an acid value of 100 KoHmg/g, a double bondequivalent (the resin weight per 1 mol of unsaturated groups) of 450,and a weight average molecular weight of 20,000.

Subsequently, a resist layer pattern was likewise formed as in theExample 4 using a mixture composed of 100 parts of the resin solution,150 parts of the resin solution in the Synthesis Example 1, 15 parts ofthe compound (C), and 5 parts of benzoin ethylether.

Comparative Example 4

The same operations were followed as in the Example 4, except that 150parts of the resin solution in the Synthesis Example 1 was replaced with130 parts of "Silica sol IPA-ST" to form a resist pattern layer.

Comparative Example 5

The same operations were followed as in the Example 4, except that theresin solution in the Synthesis Example 3 was employed by replacing withthe resin solution in the Synthesis Example 1 to form a resist patternlayer. Table 4 collectively shows experimental results for properties ofthe layers in the Comparative Examples 4 and 5. ##STR11##

                  TABLE 4                                                         ______________________________________                                                                  Compative                                                                              Compative                                    Example Example Example Example                                               4 5 6 7                                                                     ______________________________________                                        Developability (90                                                                        ⊚                                                                       ⊚                                                                       ⊚                                                                     ⊚                           seconds)                                                                      Developability (180 ⊚ ⊚ ⊚                                           ⊚                           seconds)                                                                      Finger-touch O ⊚ O O                                           dryability                                                                    Cross-hatched 100/100 100/100 50/100 60/100                                   adhesion                                                                      Acid resistance ⊚ ⊚ ▴                                               ▴                           Solder resistance *1 normal normal normal normal                              Solder resistance *2 4 4 blister blister                                      Solder resistance *3 100/100 100/100 0/100 0/100                              Immersion test for 100/100 100/100 0/100 1/100                                hot water resistance                                                        ______________________________________                                         *1: Results of visual observation after 3 cycles in Solder resistance tes     *2: Results of visual observation after 6 cycles in Solder resistance tes     *3: Results of crosshatched adhesion after 6 cycles in Solder resistance      test                                                                     

METHODS FOR MEASURING

(1) Pencil hardness: It was conducted according to JIS K5400.

(2) Cross-hatched adhesion: 100 pieces of cross-cuts having an intervalof 1 mm were formed on the surface of a layer with a cutter and, acellophane tape was adhered to the cross-cuts, and adhesive conditionsof the layer were observed after abruptly stripping. Results are shownby "the number of the cross-cuts remained/the number of the cross-cutsformed".

(3) Thermocycle test: 50 cycles were repeated to a cast article, inwhich 1 cycle is repetition of heating at 150° C. for 5 hours andcooling at -20° C. for 5 hours. Evaluation was visually conducted.

(4) Developability: It was conducted by spraying a developer (1.5 Na₂CO₃ aqueous solution) at 25° C. and spraying pressure of 2 kg/cm₂ for afixed time (90 seconds and 180 seconds) onto a resist layer afterexposed. Evaluations are shown by ⊚: being capable of developing throughan inside of through holes, o: being capable of completely developingthe surface of the board, ▾: there are caused defects in resist patternssuch as portions which are incapable of developing the surface of a baseplate or portions eroded or swelled by the developer, and x: beingalmost incapable developing.

(5) Finger-touch dryability: Film was closely adhered to a coating layerwith a vacuum laminator, followed by visually observing after exposed.Evaluation standards are as follows, ⊚: the film is not quite stained bythe coating layer, o: the film is slightly stained by the coating layer,x: the film is clearly stained by the coating layer.

(6) Acid resistance: It was visually observed after immersed in 1N H₂SO₄ at 60° C. for 1 hour, and it is shown by, ⊚: conditions do not quitechange in coating layer, o: blistering and change of color are slightlyobserved in conditions of coating layer, ▾: change of color is clearlyobserved in conditions of coating layer, and x: coating layer isdissolved or peeled.

(7) Solder resistance (visual observation): Test pieces were floatedaccording to JIS C6481 on a solder bath of 260° C. for 10 seconds as 1cycle, and those were observed at third cycle and sixth cycle, followedby visually evaluating.

(8) Solder resistance (cross-hatched adhesion): Test pieces were floatedaccording to JIS C6481 on a solder bath of 260° C. for 10 seconds as 1cycle, and 100 pieces of cross cuts having an interval of 1 mm wereformed on a coating layer with a cutter and, a cellophane tape wasadhered to the cross cuts after sixth cycle, and adhesive conditions ofthe coating layer were observed after abruptly stripping. Results areshown by "the number of the cross-cuts remained/the number of thecross-cuts formed".

(9) Immersion test for boiled water resistance: After test pieces wereimmersed in hot water of 80-90° C. for 1 hour, and 100 pieces of crosscuts having an interval of 1 mm were formed on a layer with a cutterand, a cellophane tape was adhered to the cross cuts, and adhesiveconditions of the layer were observed by abruptly stripping. Results areshown by "the number of the cross-cuts remained/the number of thecross-cuts formed".

POSSIBILITES OF UTILIZATION IN INDUSTRY BY THE THIRD ASPECT OF THEINVENTION

In the active energy ray-polymerizable unsaturated resin composition ofthe present invention, there can be readily conducted a reaction of thealicyclic epoxy group in the unsaturated compound (E) containing analicyclic epoxy group with a silanol group in the colloidal silica (F)component in the presence of the metal compound (G) which is a catalyst.And, since a bond of the colloidal silica (F) with a polymerizableunsaturated group connects to the colloidal silica (F) through thealicyclic epoxy group, a layer composed of "curable composition"prepared using "resin composition" obtained is excellent in heatresistance and chemical resistance and, further, it is excellent infinishing and transparency, etc.

TECHNICAL FIELD OF FOURTH ASPECT OF THE INVENTION

The fourth aspect of the invention relates to a low temperature-curableresin composition and, in more detail, it relates to a lowtemperature-curable resin composition, which is a composition composedof a vinyl copolymer of a monomer having a polysiloxane structure with avinyl monomer having a specified structure containing an oxirane group,a specified metal compound, and a specified compound containing at leasttwo alicyclic oxirane groups, and which does not require water componentin a curing reaction, and which is excellent in a low temperaturecurability and storage stability, and in which shrinkage is not causedbecause of a small difference in curability between the surface andinside, and which can provide a cured article having excellentweatherability and water resistance.

BACKGROUND ART OF FOURTH ASPECT OF THE INVENTION

In order to reduce energy costs, there has been intensively desired adevelopment of a resin composition which is curable at low temperature.Heretofore, as a low temperature-curable resin composition, there hasbeen mainly employed a two-liquid type resin composition such as apolyol/isocyanate system and an epoxy/polyamine system. However, in suchthe two-liquid type resin composition, since two components must bemixed immediately before employing, handling is troublesome. Further, inthe case that an isocyanate is employed, there is a disadvantage ofsevere toxicity. On the other hand, although there is also known anactive energy ray-curable-type and one-liquid type polymerizableunsaturated resin composition to be cured by an ultraviolet ray and anelectronic beam, and the like, since an irradiation apparatus isindispensable, it is not regarded that operability is good. Stillfurther, as a low temperature-curable resin composition which is aone-liquid type and does not require the irradiation apparatus, there isdisclosed a composition in which an aluminum chelate compound is mixedin a vinyl polymer containing an alkoxysilane such as methacryloxypropyltrimethoxysilane, for example, in JP-A-60067553 Official Gazette.

However, since the composition in the above-described Official Gazettecontains a silanol group alone which is generated by hydrolysis of thealkoxysilane group as a curable functional group, it requires a largeamount of water in curing.

Also, physical properties in a cured article are not sufficient by thepresence of a large amount of by-products such as alcohols which aregenerated in hydrolysis. Further, in the case that curing is conductedby moisture alone in air, because curing initiates at the surface, innerportions are not apt to be readily cured, whereby, there is a problemthat shrinkage is apt to be caused in a cured article.

DISCLOSURE OF FOURTH ASPECT OF THE INVENTION

The present inventor, as a result of repeated intensive investigationsfor solving the problems in prior arts, has found that a silanol groupand oxirane group which exist in a composition obtained act as a curablefunctional group by mixing a vinyl copolymer containing a specifiedpolysiloxane-based macromonomer and a vinyl monomer having a specifiedvinyl monomer containing an oxirane group with a specified compoundcontaining an alicyclic oxirane group and a specified organic metalcompound and, whereby, the composition can be cured even at lowtemperatures of not more than 100° C., and shrinkage is slight because acuring reaction simultaneously progresses in the surface and insideportions of a cured article, and the present invention has beencompleted.

That is, the present invention provides a low temperature-curable resincomposition characterized by containing the components (a), (b), and (c)described below.

(a) a vinyl copolymer having a number average molecular weight of2,000-100,000 which is a copolymer of a polysiloxane-based macromonomerhaving a number average molecular weight of 400-50,000 containing atleast two hydroxyl groups or alkoxyl groups in the molecule with a vinylmonomer containing oxirane group represented by formula (6) describedbelow, and the macromonomer is obtained by allowing to react 70-99.999%by mol of a compound (H) represented by formula (7) described below with30-0.001% by mol of a compound (J) represented by formula (8) describedbelow, (b) a 6-coordinated organic aluminum chelate compound and/or an8-coordinated organic zirconium chelate compound, and (c) a compoundhaving a number average molecular weight of not more than 1,000containing at least two alicyclic oxirane groups in the molecule.Hereinafter, the present invention is illustrated in detail.

    R.sup.11 --SiR.sup.12 R.sup.13 R.sup.14                    (7)

(in the formula, R¹¹ represents an aliphatic hydrocarbon group having acarbon number of 1-8 or a phenyl group, and R¹², R¹³, and R¹⁴ representan alkoxyl group having a carbon number of 1-4 or a hydroxyl group),

    CH.sub.2 ═CR.sup.15 COO(CH.sub.2).sub.k --SiR.sup.16 R.sup.17 R.sup.18 (8)

(in the formula, R¹⁵ represents a hydrogen atom or a methyl group, R¹⁶,R¹⁷, and R¹⁸ represent any one of a hydroxyl group, an alkoxyl grouphaving a carbon number of 1-4, and an aliphatic hydrocarbon group havinga carbon number of 1-8, "k" is an integer of 1-6, and all the R¹⁶, R¹⁷,and R¹⁸ are not simultaneously an aliphatic hydrocarbon group having acarbon number of 1-8),

    R.sup.2 --O--CO--NH--CH═CH--R.sup.1                    (6)

(in the formula, R¹ represents a hydrogen atom, an aromatic hydrocarbongroup, or a saturated or unsaturated aliphatic hydrocarbon group, and R²represents formula (2) or (3)), ##STR12## (in the formula, R⁴ and R⁵represent a hydrogen atom, a methyl group or ethyl group, respectively,"m" represents an integer of 4-8, and "n" represents an integer of1-10).

BEST MODE FOR CARRYING OUT THE FOURTH ASPECT OF THE INVENTION COMPONENT(A)

The component (a) to be employed for the low temperature-curable resincomposition of the present invention is a vinyl copolymer containing apolysiloxane-based macromonomer and a vinyl monomer containing oxiranegroup represented by the formula (6) as monomer components. In thecomponent (a), a number average molecular weight ranges in 2,000-100,000and, particularly, preferably in 4,000-50,000. In the case of less than2,000, curability is poor and, on the other hand, in the case that thenumber average molecular weight is more than 100,000, there lowerworkability in coating and compatibility with the compound containingoxirane group which is the component (c).

POLYSILOXANE-BASED MACROMONOMER

The polysiloxane-based macromonomer which constitutes the component (a)is characterized in that it has a polysiloxane structure, and in whichthere connect to Si an alkoxyl group including an aliphatic hydrocarbongroup, a phenyl group, hydroxyl group, an alkoxyl group, and an alkoxylgroup containing a polymerizable carbon-carbon double bond, and thelike, and which has at least two silanol groups or alkoxy silane groupsin the molecule which connect to Si in the polysiloxane structure.

The polysiloxane-based macromonomer to be employed in the presentinvention can be prepared by a reaction of the compound (H) representedby the above-described formula (7) with the compound (J) represented bythe above-described formula (8).

The compound (H) is represented by the above-described formula (7). Inthe formula, R¹¹ represents an aliphatic hydrocarbon group having acarbon number of 1-8 or a phenyl group, and there can be exemplifiedlinear or branched groups such as methyl group, ethyl group, propylgroup, butyl group, pentyl group, hexyl group, heptyl group, and octylgroup. As the R¹¹, there are particularly preferred methyl group andphenyl group. R¹², R¹³, and R¹⁴ represent an alkoxyl group having acarbon number of 1-4 or a hydroxyl group, and which may be all identicalor partially or wholly different from each other. As the alkoxyl grouphaving a carbon number of 1-4, there can be exemplified linear orbranched groups such as methoxy group, ethoxy group, propoxy group, andbutoxy group. As the R¹², R¹³, and R¹⁴, there are particularly preferredmethoxy group, ethoxy group, propoxy group, butoxy group, and hydroxylgroup.

Specifically, as the compound (H), there can be exemplified methyltrimethoxysilane, phenyl trimethoxysilane, butyltrimethoxy silane,methyl triethoxysilane, methyl tributhoxysilane, phenyltrisilanol, andmethyltrisilanol, etc. Of those, there are particularly preferred methyltrimethoxysilane, phenyl trimethoxysilane, and phenyltrisilanol. In thepresent invention, these can be employed one kind or two or more kindsof those.

The compound (J) is represented by the above-described formula (8). Inthe formula, R¹⁵ represents a hydrogen atom or a methyl group, R¹⁶, R¹⁷,and R¹⁸ represent any one of a hydroxyl group, an alkoxyl group having acarbon number of 1-4, and an aliphatic hydrocarbon group having a carbonnumber of 1-8, "k" represents an integer of 1-6. Although R¹⁶, R¹⁷, andR¹⁸ may be all identical or partially or wholly different from eachother, all of them must not be simultaneously an aliphatic hydrocarbongroup having a carbon number of 1-8. Because it cannot connect to thecompound (H). As the aliphatic hydrocarbon group having a carbon numberof 1-8 and alkoxyl group having a carbon number of 1-4, there can beemployed the same groups as exemplified in the compound (H). It is to benoted that as R¹⁶, R¹⁷, and R¹⁸, there are preferred methoxy group,ethoxy group, and hydroxyl group and, as "n", a range of 2-4 isparticularly preferred.

As the compound (J), there can be exemplified γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyl triethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-methacryloxybutyl triethoxysilane, andγ-acryloxypropyl trisilanol, and the like. Of those, there areparticularly preferred γ-methacryloxypropyl trimethoxysilane,γ-methacryloxypropyl triethoxysilane, and γ-acryloxypropyl trisilanol.In the present invention, these can be employed one kind or two or morekinds thereof.

The polysiloxane-based macromonomer can be prepared by allowing to reactafter mixing the above-described compounds (H) and (J). As mixing ratioin the both compounds, the compound (H) ranges in 70-99.999% by mol,preferably 90-99.9% by mol, and more preferably 95-99% by mol, and thecompound (J) ranges in 30-0.001% by mol, preferably 10-0.1% by mol, andmore preferably 5-1% by mol. In the case that the compound (H) is lessthan 70% by mol, gelation is apt to be caused in a copolymerizationreaction and, on the other hand, in the case of exceeding 99.999% bymol, there increases the amount of the polysiloxane which does notcopolymerize, unpreferably resulting in that a resin solution becomescloudy.

The reaction between the compounds (H) and (J) is a condensationaccompanied by dehydration of hydroxyl groups in the both compounds orhydroxyl groups produced by hydrolysis of the alkoxyl group. In thecase, there occurs not only the condensation accompanied by dehydrationbut also a condensation accompanied by removal of an alcohol dependingupon reaction conditions. Although the reaction may be conducted withoutsolvents, there are preferably employed organic solvents or water whichcan dissolve the compounds (H) and (J).

As the organic solvents to be employed, there can be exemplifiedhydrocarbon-based solvents such as heptane, toluene, xylene, octane, andmineral spirits, ester-based solvents such as ethyl acetate, n-butylacetate, isobutyl acetate, methylcellosolve acetate, and butylcarbitolacetate, ketone-based solvents such as methylethyl ketone,methylisobutyl ketone, and diisobutyl ketone, alcohol-based solventssuch as ethanol, isopropanol, n-butanol, sec-butanol, and isobutanol,ether-based solvents such as n-butylether, dioxane, ethylene glycolmonomethylether, and ethylene glycol monoethylether, and the like. Therecan be employed one kind or two or more kinds of these. It is to benoted that in the case of employing in a solution state, theconcentration of the compounds (H) and (J) is preferably not less than5% by weight based on the total amount of both.

In the reaction between the compounds (H) and (J), temperature is20-180° C. and, particularly, preferably 50-120° C.

Also, the reaction time is preferably 1-40 hours. In the reaction, apolymerization inhibitor can be optionally added.

The use of the polymerization inhibitor is effective for preventingpolymerization of an unsaturated bond contained in the compound (J)during the reaction with the compound (H) and, for example, there can beemployed hydroquinone and hydroquinone monomethylether, and the like. Itis to be noted that in the preparation of the polysiloxane-basedmacromonomer, not more than 20% by mol of tetraalkoxy silane or dialkyldialkoxy silane can be added based on 100% by mol of the total amount ofthe compounds (H) and (J) in a reaction system.

In the compounds (H) and (J) to be employed, in the case of a compoundin which R¹², R¹³, R¹⁴, R¹⁶, R¹⁷, and R¹⁸ are all hydroxyl group,condensation reaction accompanied by dehydration is preferably conductedwhile agitating and heating an organic solvent during the reaction. Onthe other hand, in the case of a compound in which either the compound(H) or (J) to be employed, or both have an alkoxyl group, hydrolysis ispreferably conducted prior to the condensation. Usually, a hydrolysisreaction and a reaction for bonding are continuously conducted whileheating and agitating in the presence of water and a catalyst. Althoughthe use amount of water in the case is not particularly limited, thereis preferred not less than 1 mol based on 1 mol of the alkoxyl group. Inthe case of being less than 1 mol, it is anxious that there lowers thereaction between the both compounds. There is most preferred a method inwhich excessively large amount of water is employed as a solvent.

In the hydrolysis reaction, even in the case of formation of awater-insoluble alcohol by the condensation, a reaction system can behomogenized by using water together with a water-soluble organicsolvent. As the water-soluble organic solvent to be employed, there canbe employed solvents such as an alcohol-based, ester-based, ether-based,and ketone-based one which are employed for dissolving theabove-described compounds (H) and (J).

Further, in the hydrolysis reaction, catalysts can be employed. As thecatalysts to be employed, there can be employed acid catalysts or alkalicatalysts. As the acid catalysts, there can be exemplified hydrochloricacid, sulfuric acid, phosphorus acid, formic acid, acetic acid,propionic acid, acrylic acid, and methacrylic acid, and the like. As thealkali catalysts, there can be exemplified sodium hydroxide,triethylamine, and ammonia, and the like. Addition amount of thecatalysts is preferably 0.0001-5% by weight, particularly, 0.01-0.1% byweight based on total amount of the above-described compounds (H) and(J).

Structure of a polysiloxane portion in the polysiloxane-basedmacromonomer may be a linearlike, a ladderlike, and a mixed system. Inthe present invention, of those, there are preferred the ladderlike andmixed system of the linearlike and ladderlike systems and, particularly,there is preferred one having a large amount of the ladderlike portionin view of water resistance, heat resistance, and weatherability, andthe like. The structure of the polysiloxane-based macromonomer can befreely selected by a mixing proportion of the compounds (H) and (J),mixing amount of water and the acid catalyst, and the like. In thepolysiloxane-based macromonomer to be employed in the present invention,a number average molecular weight is 400-50,000 and, particularly,preferably 1,000-20,000. In the case of less than 400, gelation tends tobe caused in copolymerization and, in the case of exceeding 50,000,miscibility tends to lower.

Also, the polysiloxane-based macromonomer in a liquid by the reaction ofthe compound (H) with the compound (J) contains a polymerizableunsaturated bond of preferably 0.2-1.9 piece, more preferably 0.6-1.4piece and, particularly 0.9-1.2 piece in the molecule. In the case thatthe polymerizable unsaturated bond is excessively less, whitening is aptto be caused in a copolymerized reaction product between thepolysiloxane-based macromonomer and a vinyl monomer having oxiranegroup. On the other hand, in the case that the polymerizable unsaturatedbond is excessively more, gelation is unpreferably apt to be caused incopolymerization reaction. The number of unsaturated bond in thepolysiloxane-based macromonomer is obtained by the following methods.

(1) A variety of polysiloxane-based macromonomers are obtained byappropriately changing the proportion of the compounds (H) and (J), andby allowing to react in identical conditions.

(2) A variety of vinylcopolymers are prepared by allowing to react therespective monomers obtained with a nonfunctional vinyl monomer bychanging the proportion to be employed.

(3) Molecular weight distribution in the vinylcopolymers obtained ismeasured by a gel permeation chromatography (G.P.C.).

(4) Even in the case that there is changed the proportion of thepolysiloxane-based macromonomer to the nonfunctional monomer to beemployed, a peak molecular weight (a molecular weight of a most largecontent) in the copolymer obtained is nearly identical, and adistribution curve is a monopeak and, in the case that there are notobserved a distribution of components having a low molecular weight (amonomer not having an unsaturated bond component) and a distribution ofcomponents having a high molecular weight (a copolymer of a monomerhaving at least two unsaturated bonds), the monomer has one piece ofpolymerizable unsaturated bond in the molecule on an average.

(5) In other macromonomer, when use amount by mol number of the compound(H) is [H], and use amount by mol number of the compound (J) is [J], inthe case of employing the macromonomer having 1 piece of a polymerizableunsaturated bond on an average, when the mol number of the compound (H)is [H1], and the mol number of the compound (J) is [J1], the averagenumber of the macromonomer having a polymerizable unsaturated bond inthe macromonomer is measured by [J]/[H] and [J1]/[H1].

(6) For example, if there is obtained a macromonomer having the numberof the polymerizable unsaturated bond of 1 piece in the case of thecompound (J)/the compound (H)=1/20 (molar ratio), in the case of thecompound (J)/the compound (H)=0.9/20, the number of the polymerizableunsaturated bond becomes 0.9 piece on an average in the macromonomer.

VINYL MONOMER CONTAINING OXIRANE GROUP

The vinyl monomer containing oxirane group which constitutes thecomponent (a) is a compound represented by the formula (6) and, it isprepared by the same preparation process, and has the same structuralformula as a compound having R² represented by the formula (2) or (3) inthe compound represented by the formula (1) which is the first aspect ofthe invention.

Also, as the vinyl monomer containing oxirane group in the presentinvention, there can be employed together a monomer containing glycidylgroup such as glycidylmethacrylate, glycidylacrylate, and vinylglycidylether, and the "any one of other alicyclic epoxy compounds containing anunsaturated group" in the second aspect of the invention. Of those, themonomer containing glycidyl group is preferred in view of capability ofreadily obtaining and costs, and the monomer containing alicyclicoxirane group is preferably employed in view of curability of the lowtemperature-curable resin composition. These can be employed in a rangeof 0-80% by mol of the vinyl monomer containing oxirane group to beemployed.

The component (a) to be employed for the low temperature-curable resincomposition of the present invention is a vinyl copolymer in which thereare employed the polysiloxane-based macromonomer and the vinyl monomercontaining oxirane group as monomer components. In the copolymer, otherpolymerizable vinyl monomers can be optionally employed other than theabove-described monomer components as monomer components. As the otherpolymerizable vinyl monomers to be employed, the following compounds areexemplified.

(a) Esters of acrylic acid or methacrylic acid: for example, alkylesters having a carbon number of 1-18 of acrylic acid or methacrylicacid such as methyl acrylate, ethyl acrylate, propyl acrylate, isopropylacrylate, butyl acrylate, hexyl acrylate, octyl acrylate, laurylacrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate,isopropyl methacrylate, butyl methacrylate, hexyl methacrylate, octylmethacrylate, and lauryl methacrylate; alkoxyalkyl esters having acarbon number of 2-18 of acrylic acid or methacrylic acid such asmethoxybutyl acrylate, methoxybutyl methacrylate, methoxyethyl acrylate,methoxyethyl methacrylate, ethoxybutyl acrylate, and ethoxybutylmethacrylate; alkenyl esters having a carbon number of 2-18 of acrylicacid or methacrylic acid such as allyl acrylate and allyl methacrylate;hydroxyalkyl esters having a carbon number of 2-18 of acrylic acid ormethacrylic acid such as hydroxyethyl acrylate, hydroxyethylmethacrylate, hydroxypropyl acrylate, and hydroxypropyl methacrylate;alkenyloxyalkyl esters having a carbon number of 3-18 of acrylic acid ormethacrylic acid such as allyloxyethyl acrylate and allyloxyethylmethacrylate.

(b) Vinyl aromatic compound: for example, styrene, α-methylstyrene,vinyltoluene, and p-chlorostyrene.

(c) Diene-based compound: for example, butadiene, isoprene, andchloroprene.

(d) Others: acrylonitrile, methacrylonitrile, methyl isopropenyl ketone,Beova monomer of vinyl acetate (a product of Shell Kagaku, Ltd.), vinylpropionate, and vinyl pivarate, and the like.

As copolymerization proportion of the polysiloxane-based macromonomerwith respect to the vinyl monomer containing oxirane group, thepolysiloxane-based macromonomer is 0.01-98% by weight, the vinyl monomercontaining oxirane group is 99.99-2% by weight, more preferably, thepolysiloxane-based macromonomer is 0.1-80% by weight, and the vinylmonomer containing oxirane group is 99.9-20% by weight. In the case thatthe polysiloxane-based macromonomer is less than 0.01% by weight,curability lowers, and, in the case of exceeding 98% by weight, physicalproperties lower in a cured article, and there is shown a tendency beingapt to cause a shrinkage. Also, in the case that the other polymerizablevinyl monomers are employed in addition to the above-described two kindsof monomers as monomer components, the polysiloxane-based macromonomeris 0.01-80% by weight, the vinyl monomer containing oxirane group is90-1% by weight, other polymerizable vinyl monomers are more than 0 andnot more than 98.99% by weight, and more preferably thepolysiloxane-based macromonomer is 0.1-60% by weight, the vinyl monomercontaining oxirane group is 60-3% by weight, and the other polymerizablevinyl monomers are 10-96.9% by weight. In the case that the use amountof the polysiloxane-based macromonomer and the vinyl monomer containingoxirane group ranges in the scope, no shrinkage is preferably caused.

The above-described vinyl copolymer can be obtained by the same methodsand the same conditions as in a synthesis reaction for usual acrylicresins and vinyl resins, and the like. For example, there can beexemplified a method in which respective monomer components aredissolved or dispersed into an organic solvent, and then heated attemperature of 60-180° C. or so under the presence of a radicalpolymerization initiator while agitating. Reaction time of period ispreferably 1-10 hours.

Further, as the organic solvent, there can be exemplified the samealcohol-based solvents, ether-based solvents, ester-based solvents, andhydrocarbon-based solvents, and the like as described in the reactionbetween the above-described (H) and (J). In the case that thehydrocarbon-based solvents are employed, those are preferably employedtogether with other solvents in view of solubility.

In a reaction system, a radical initiator can be employed and, as anexample, there are shown peroxides such as benzoyl peroxide andt-butylperoxy-2-ethylhexanoate, and azo-compounds such asazoisobutylnitrile and azobisdimethyl valeronitrile.

COMPONENT (B)

The component (b) to be employed in the present invention is a6-coordinated organic aluminum chelate compound and/or an 8-coordinatedorganic zirconium chelate compound, and there can be exemplified thefollowing compounds.

As the 6-coordinated organic aluminum chelate compound, there ispreferred a compound obtained by treating an organic aluminum with achelating agent. As the organic aluminum, there is preferred a compoundshown by the formula (9) described below.

    R.sup.20 --AlR.sup.21 R.sup.22                             (9)

(in the formula, at least one of R²⁰, R²¹, and R²² represent an alkoxylgroup having a carbon number of 1-13 or an alkoxyalkoxyl group having acarbon number of 3-10, and other groups represent any of an alkyl grouphaving a carbon number of 1-6, an aryl group, an alkenyl group, and analkyl group having a carbon number of 1-6 substituted by mercapto groupor amino group)

In the formula (9), as the alkoxyl group having a carbon number of 1-13in R²⁰, R²¹, and R²², there can be exemplified methoxy, ethoxy,n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy,n-pentoxy, isoamyloxy, n-hexyloxy, n-heptyloxy, and n-octyloxy. As thealkoxyalkoxyl group having a carbon number of 3-10, there can beexemplified methoxymethoxy, methoxyethoxy, ethoxybutoxy, andbutoxypentoxy, and the like.

Further, as the alkyl group having a carbon number of 1-6, there can beexemplified methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl,sec-butyl, tert-butyl, and amyl group, as the aryl group, there can beexemplified phenyl or toluyl group, and, as the alkenyl group, there canbe exemplified vinyl or allyl group. Still further, as an alkyl grouphaving a carbon number of 1-6 substituted by mercapto group or aminogroup, there can be exemplified γ-mercaptopropyl group, aminoethylgroup, aminopropyl group, and aminobutyl group.

As the preferred 6-coordinated organic aluminum chelate compound, therecan be exemplified aluminum isopropylate, aluminum sec-butylate, andaluminum tert-butylate, and the like.

On the other hand, as the chelating agent to be allowed to react withthe above-described organic aluminum, there can be exemplified loweralkanol amines, for example, triethanolamine, diethanolamine, anddimethylaminoethanol, and the like, an acetoacetate, for example,acetomethylacetate and acetoethylacetate, and the like, a diketonealcohol, for example, diacetone alcohol, and the like, diketones, forexample, acetylacetone, and the like, glycols, for example, ethyleneglycol and octylene glycol, and the like, an oxycarboxylic acid, forexample, lactic acid and tartaric acid, and the like, a dicarboxylicacid or an ester thereof, for example, maleic acid, ethyl malonate, andthe like, and salicylic acid, cathecol, and pyrogallol, and the like. Ofthose, there are preferred the lower alkanol amines, the oxycarboxylicacid, and the diketones.

As the preferred 6-coordinated organic aluminum chelate compound to beemployed in the present invention, there are preferred compounds nothaving hydroxyl group and an alkoxyl group which directly connect toaluminum atom. In the case that the organic aluminum chelate compoundhas hydroxyl group and an alkoxyl group which directly connect toaluminum atom, by mixing it with the low temperature-curable resincomposition of the present invention, storage stability of a compositionbecomes unpreferably poor, and smoothness in a coating layer isunpreferably occasionally lowered after curing.

As the preferred 6-coordinated organic aluminum chelate compound to beemployed in the present invention, there can be exemplified aluminumtris(ethylacetoacetate), tristrifluoro acetylacetonate aluminum,trishexafluoro acetylacetonate aluminum, trisethylacetoacetate aluminum,tris(n-propyl acetoacetate)aluminum, tris(iso-propylacetoacetate)aluminum, tris(n-butylacetoacetate)aluminum, trissalycilicaldehydate aluminum, tris(2-ethoxycarbonylphenolate)aluminum,tris(acetyl acetonate)aluminum, tris(ethylacetonate)aluminum, andtris(salicylicaldehydate)aluminum, and the like, and these may bepartially condensed.

As the preferred 8-coordinated organic zirconium chelate compound to beemployed in the present invention, there are preferred compoundsobtained by treating an organic zirconium with a chelating agent, and asthe organic zirconium, there is preferred a compound represented by theformula (10) described below,

    R.sup.23 --ZrR.sup.24 R.sup.25 R.sup.26                    (10)

(in the formula, at least any two of R²³, R²⁴, R²⁵, and R²⁶ represent analkoxyl group having a carbon number of 1-13 or an alkoxyalkoxyl grouphaving a carbon number of 3-10, and other groups represent any one of analkyl group having a carbon number of 1-6, an aryl group, an alkenylgroup, and an alkyl group having a carbon number of 1-6 substituted bymercapto group or amino group).

In the formula (10), as the alkoxyl group having a carbon number of1-13, there can be exemplified methoxy, ethoxy, n-propoxy, isopropoxy,n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, isoamyloxy,n-hexyloxy, n-heptyloxy, and n-octyloxy. As the alkoxyalkoxyl grouphaving a carbon number of 3-10, there can be exemplified methoxymethoxy,methoxyethoxy, ethoxybutoxy, and butoxypentoxy, and the like. Further,as the alkyl group having a carbon number of 1-6, there can beexemplified methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl,sec-butyl, tert-butyl, and amyl group, as the aryl group, there can beexemplified phenyl or toluyl group, and, as the alkenyl group, there canbe exemplified vinyl or allyl group.

Still further, as the alkyl group having a carbon number of 1-6substituted by mercapto group or amino group, there can be exemplifiedγ-mercaptopropyl group, aminoethyl group, aminopropyl group, andaminobutyl group.

As the preferred organic zirconium, there can be exemplified tetramethylzirconate, tetraethyl zirconate, tetraisopropyl zirconate, tetra-n-butylzirconate, tetraisobutyl zirconate, and tetra-tert-butyl zirconate, andthe like.

As the chelating agent to be allowed to react with the above-describedorganic zirconium compound, there can be preferably employed the samecompounds as the chelating compound to be employed in the case of the6-coordinated organic aluminum compound described hereinabove.

As the organic zirconium chelate compound to be employed in the presentinvention, there is preferred a compound not having hydroxyl group andan alkoxyl group which directly connect to zirconium atom. In the caseof having the hydroxyl group and an alkoxyl group which directly connectto zirconium atom, as well as in the case of the aluminum compounds,there are unpreferably caused a decline of storage stability in a resincomposition and a decline of smoothness in a cured coating layer.

As the 8-coordinated organic zirconium chelate compound, there can beexemplified tetraxis(oxalic acid)zirconium,tetraxis(acetylacetone)zirconium,tetraxis(n-propylacetoacetate)zirconium, tetraxis(ethylacetoacetate)zirconium, and tetraxis(salicylic aldehydate) zirconium, and the like,and these may be partially condensed.

COMPONENT (C)

The component (c) to be employed in the present invention is a compoundhaving at least two alicyclic oxirane groups in the molecule and havinga number average molecular weight of not more than 1,000, and there canbe exemplified compounds described below.

(i) There are compounds shown below including the compound (K).##STR13##

(ii) There is an adduct of 3,4-epoxycyclohexylmethyl alcohol, and thelike with a polyisocyanate compound.

As the polyisocyanate compound to be employed, there can be exemplified,for example, an organic diisocyanate itself which includes aliphaticdiisocyanates such as hexamethylene diisocyanate ortrimethylhexamethylene diisocyanate, alicyclic diisocyanates such asxylilene diisocyanate or isophorone diisocyanate, aromatic diisocyanatessuch as tolylene diisocyanate or 4,4'-diphenylmethane diisocyanate, oran adduct of the respective diisocyanates with a polyvalent alcohol, apolyester resin having a low molecular weight, or water, a polymer ofthe above-described respective diisocyanates themselves and, further, anisocyanate-buret compound, and the like. As commercially suppliedproducts, there are "Vernok DN-950", "Vernok D-970", or "Vernok D15-455"which are products manufactured by Dainippon Ink Kagaku, Ltd.,"Desmodule L", "Desmodule NHL", "Desmodule IL", or "Desmodule N3390"which are products manufactured by Bayer, AG. in Germany, "TakenateD-102", "Takenate D-202", or "Takenate D-123N" which are productsmanufactured by Takeda Yakuhin Kogyo, Ltd., "Coronate L", "Coronate HL","Coronate EH" or "Coronate 203" which are products manufactured by NihonPolyurethane Kogyo, Ltd., and "Duranate 24A-90CX" which is a productmanufactured by Asahi Kasei Kogyo, Ltd.

(iii) There are adducts of the above-described compound (K) with apolybasic acid.

(iv) There are an esterified product having an unsaturated bond in themolecule, for example, such as 4-cyclohexene-1,2-ilene, and a compoundwhich is obtained by oxidation of an esterified compound having a numberaverage molecular weight of 900 which is obtained by an esterificationreaction of, for example, tetrahydrophthalic anhydride,trimethylolpropane, and 1,4-butanediol, and the like with peraceticacid, and the like.

Further, as the above-described compound having alicyclic oxirane group,there can be also employed a compound into which there is introducednon-alicyclic oxirane group other than the alicyclic oxirane group.

As a molecular weight of the component (c), it is important that it isnot more than 1,000 in a number average molecular weight. In the casethat the number average molecular weight exceeds 1,000, there lowersmiscibility with the vinyl copolymer resin which is the component (c) tobe mixed into the low temperature-curable resin composition of thepresent invention, resulting in that there cannot be formed a coatinglayer which is excellent in a finishing property and coatability.

LOW TEMPERATURE-CURABLE RESIN COMPOSITION

The low temperature-curable resin composition of the present inventionis composed of the components (a), (b), and (c).

Mixing amount of the component (b) is preferably 0.01-30 parts by weightbased on 100 parts by weight of the component (a), in particular, it ispreferably 0.1-15 parts by weight. In the case that use amount of thecomponent (b) is less than the range, there is shown a tendency ofdecline in crosslinking curability and, in the case that it is more thanthe range, it remains in a cured article, and water resistanceunpreferably lowers in the cured article.

Mixing amount of the component (c) is preferably 0.1-1,000 parts byweight based on 100 parts by weight of the component (a), and it is morepreferably 5-100 parts by weight. In the case of less than 0.1 part byweight, the content of alicyclic oxirane groups lowers which is animportant factor for accelerating curability. Further, the component (c)has a role as a diluent in the low temperature-curable resincomposition, and it also contributes to an increase or decrease of thesolid content in the low temperature-curable resin composition, and itis desirably mixed in not less than 0.1 part by weight from theviewpoint. It is to be noted that in the case that the mixing amount ofthe component (c) becomes more than 1,000 parts by weight, curabilitylowers because of decline in the content of SiOR or/and SiOH groups inthe low temperature-curable resin composition.

OTHER COMPONENTS

In the resin composition of the present invention, there can be furtheroptionally mixed, for example, a resin containing epoxy groups ("Epikote1001" manufactured by Shell Kagaku) and a resin containing hydroxylgroups such as a styrene-allylalcohol copolymer. The resins can be mixedin a mixing amount of not more than 10% by weight based on the lowtemperature-curable resin composition of the present invention.

USES

A cured article obtained from the low temperature-curable resincomposition of the present invention is excellent in weatherability andwater resistance, and the like, and it is preferably employed in usessuch as, for example, coating or repairing for cars and containers,coating for structural materials in the open air, and a precoat metal,and the like. It is to be noted that in the case of employing as acoating, coating methods are not limited, and it can be coated by aspray coating, a roll coating, and a brush coating, and the like whichare usual coating methods.

The low temperature-curable resin composition of the present inventioncan be employed by dissolving in organic solvents. As the solvents to beemployed, there are exemplified a hydrocarbon-based solvent such astoluene and xylene, a ketone-based solvent such as methylethylketone andmethylisobutylketone, an ester-based solvent such as ethyl acetate andbutyl acetate, an ether-based solvent such as dioxane and ethyleneglycoldiethylether, an alcohol-based solvent such as butanol and propanol, andthe like. The solvents can be employed solely or by appropriatelymixing, and in the case of employing the alcohol-based solvent, it ispreferably employed together with other solvents from a viewpoint ofsolubility to resins. It is to be noted that the concentration of thelow temperature-curable resin composition can be appropriately selectedaccording to the purposes of uses and, usually, it is preferably 10-70%by weight.

The low temperature-curable resin composition of the present inventioncan be readily crosslinked and cured at low temperatures of not morethan 100° C. For example, in the case that it is cured at ordinarytemperatures without any heating, it can be usually and sufficientlycured for 8 hours to 7 days or so. Further, in the case that it isheated at 40-100° C. or so, it can be sufficiently cured for 5 minutesto 3 hours or so.

Still further, even in the vicinity of ordinary temperatures, it can besufficiently cured within several tens hours.

It is thought that the curing reaction in the low temperature-curableresin composition of the present invention initiates by volatilizationof solvents, and it proceeds as a chain reaction by volatilization ofthe chelating agent from a crosslinking and curing agent. It is guessedthat proceeding of the curing reaction by the crosslinking and curingagent depends upon a mechanism as shown hereinafter. That is, in thecase that the organic aluminum chelating agents are employed as thecrosslinking and curing agent, first of all, as a first stage reactionafter volatilization of the chelating agents, an aluminum compoundreacts with the silanol group in the polysiloxane-based macromonomerstructural unit to produce the bond of the formula (11) Subsequently, asa second stage reaction, the silanol group coordinates with the bond ofthe formula (11), and it changes to the formula (12), whereby, thesilanol group is polarized. The silanol group polarized reacts withepoxy groups, and it changes to an oxonium salt as in the formula (13).Subsequently, there are caused an ionic polymerization of epoxy groupsand addition reaction to hydroxyl group. ##STR14##

It is guessed that the curing reaction in the low temperature-curableresin composition of the present invention proceeds by simultaneousoccurrence of a variety of reactions such as a condensation reaction ofsilanol groups themselves in addition to the crosslinking reaction by acatalytic action of the above-described crosslinking and curing agent.For example, it is thought that there are caused a variety of curingreactions described below.

(A) Condensation of silanol groups themselves

(B) Condensation of a silanol group with hydroxyl group produced fromoxirane group

(C) Addition of a silanol group to oxirane group

(D) Addition of hydroxyl group to oxirane group

(E) Ionic polymerization of oxirane groups themselves

It is to be noted that in the case that the polysiloxane-basedmacromonomer structural unit contains an alkoxyl group as a functionalgroup in the low temperature-curable resin composition of the presentinvention, for example, in the case that it contains an alkoxysilanegroup, although hydrolysis is required because of producing a silanolgroup, the hydrolysis reaction sufficiently proceeds by only thepresence of a slight amount of water such as moisture in air.

In the low temperature-curable resin composition of the presentinvention, in the vinyl copolymer to be employed, there exist afunctional group such as a silanol in the polysiloxane-basedmacromonomer and oxirane group in a vinyl monomer containing oxiranegroup, which are a monomer component.

Therefore, there are simultaneously caused a variety of curing reactionsas shown in the above-described (A) to (E).

As results, curing simultaneously proceeds in the surface and inside ofa cured article, and it is not apt to cause shrinkage because of a smallextent of curing in the surface and inside of a cured article.

EXAMPLES OF FOURTH ASPECT OF THE INVENTION

Hereinafter, although the present invention is specifically illustratedby Examples, the present invention is not limited by those. It is to benoted that "%" represents "% by weight" except a case particularlyshown.

Example 1

A SUS-made reaction vessel was charged with 2,720 g (20 mol) ofmethyltrimethoxysilane, 256 g (1 mol) of γ-methacryloxypropyltrimethoxysilane, 1134 g of deionized water, 2 g of 60%-hydrochloricacid, and 1 g of hydroquinone, and mixture was allowed to react at 80°C. for 5 hours. Polysiloxane-based macromonomer obtained showed a numberaverage molecular weight of 2,000, and it contained one piece of vinylgroup (a polymerizable unsaturated bond) and 4 pieces of hydroxyl groupsper 1 molecule on an average. There was added dropwise a mixturecomposed of 300 g of the macromonomer, 100 g of styrene, 280 g of acompound (D) described hereinafter, 400 g of n-butylmethacrylate, 20 gof 2,2'-azobisisobutyronitrile into 1,000 g of xylene at 120° C. topolymerize and obtain a transparent copolymer. A number averagemolecular weight was approximately 20,000. There were added 30 g of theabove-described compound (K) and aluminum tris(ethylacetoacetate) into140 g of a solution of the copolymer to coat on a glass plate so thatdried layer thickness is adjusted to 60μ, followed by baking at 90° C.for 30 minutes. Cured layer was smooth and transparent, shrinkage wasnot observed, and a residual amount was 92% after extracted by acetone.

Example 2

A SUS-made reaction vessel was charged with 7,800 g (50 mol) ofphenyltrisilanol, 200 g (1 mol) of γ-acryloxypropyl trisilanol, and4,500 g of toluene, and mixture was allowed to react at 117° C. for 3hours. Polysiloxane-based macromonomer obtained showed a number averagemolecular weight of 7,000, and it contained one piece of vinyl group and5-10 pieces of hydroxyl groups per 1 molecule on an average. There wasadded dropwise a mixture composed of 100 g of the macromonomer, 100 g of2-hydroxyethylacrylate, 200 g of a compound (L) described hereinafter,600 g of 2-ethylhexylmethacrylate, 10 g of azoisobutyronitrile into1,000 g of a mixture composed of equal weight of butanol and xylene at120° C. to polymerize and obtain a transparent copolymer. A numberaverage molecular weight was approximately 40,000.

There were added 35 g of the above-described compound (K) and 0.3 g oftetraxis(acetylacetone)zirconium into 160 g of a solution of thecopolymer to coat on a glass plate so that dried layer thickness isadjusted to 60μ, followed by baking at 80° C. for 30 minutes. Curedlayer was smooth and transparent, shrinkage was not observed, and aresidual amount was 98.4% after extracted by acetone.

Example 3

There were likewise allowed to react 48 mol of phenyltrimethoxysilaneand 2 mol of γ-methacryloxypropyl trimethoxysilane as in the Example 1.Polysiloxane-based macromonomer obtained showed a number averagemolecular weight of approximately 5,000, and it contained one piece ofvinyl group and 5-10 pieces of methoxy groups per 1 molecule on anaverage.

500 g of the macromonomer and 500 g of the vinyl monomers employed inthe Example 1 were likewise allowed to polymerize as in the Example 1 toobtain a copolymer. A number average molecular weight was approximately60,000. Into 100 g of a solution of the copolymer, there were added 50 gof an adduct of 1 mol of adipic acid with 2 mol of the above-describedcompound (K) and 1.0 g of aluminum tris(acetylacetone), and it wascoated on a glass plate so that dried layer thickness is adjusted to60μ, followed by baking at 100° C. for 30 minutes. Cured layer wassmooth and transparent, shrinkage was not observed, and a residualamount was 96% after extracted by acetone.

Example 4

There were likewise allowed to react 29.1 mol of methyl trimethoxysilaneand 0.9 mol of γ-acryloxypropyl triethoxysilane as in the Example 1.Polysiloxane-based macromonomer obtained showed a number averagemolecular weight of approximately 15,000, and it contained one piece ofvinyl group and 5-10 pieces of methoxy groups per 1 molecule on anaverage. 400 g of the macromonomer and 600 g of vinyl monomers employedin the Example 1 were likewise allowed to react as in the Example 1 toobtain a copolymer. A number average molecular weight was approximately70,000. 10 g of tetraxis (ethylacetoacetate)zirconium was added into amixture of 180 g of a solution of the copolymer with 10 g of theabove-described compound (K) to coat on a glass plate so that driedlayer thickness is adjusted to 60μ, followed by baking at 80° C. for 30minutes. Cured layer was transparent, shrinkage was not observed, and aresidual amount was 94% after extracted by acetone.

Example 5

The curable composition in the Example 2 was coated on a glass plate sothat dried layer thickness is adjusted to 60μ, followed by leaving as itis at 25° C. for 48 hours. Cured layer was transparent, shrinkage wasnot observed, and a residual amount was 95% after extracted by acetone.

Example 6

A SUS-made reaction vessel was charged with 300 g of the macromonomer inthe Example 1, 100 g of styrene, 140 g of a compound (L) describedhereinafter, 100 g of glycidyl methacrylate, 400 g ofn-butylmethacrylate, 20 g of 2,2'-azobisisobutyronitrile. Mixture wasadded dropwise into 1,000 g of xylene at 120° C. to polymerize andobtain a transparent copolymer. A number average molecular weight wasapproximately 20,000. There were added 30 g of the above-describedcompound (K) and aluminum tris(ethylacetoacetate) into 140 g of asolution of the copolymer to coat on a glass plate so that dried layerthickness is adjusted to 60μ, followed by baking at 90° C. for 30minutes. Cured layer was smooth and transparent, shrinkage was notobserved, and a residual amount was 90% after extracted by acetone.

Example 7

A SUS-made reaction vessel was charged with 300 g of the macromonomerobtained in the Example 1, 100 g of styrene, 140 g of a compound (L)described hereinafter, 140 g of a compound (M) described hereinafter,400 g of n-butylmethacrylate, 20 g of 2,2'-azobisisobutyronitrile.Mixture was added dropwise into 1,000 g of xylene at 120° C. topolymerize and obtain a transparent copolymer. A number averagemolecular weight was approximately 20,000. There were added 30 g of theabove-described compound (K) and aluminum tris(ethylacetoacetate) into140 g of a solution of the copolymer to coat on a glass plate so thatdried layer thickness is adjusted to 60μ, followed by baking at 90° C.for 30 minutes. Cured layer was smooth and transparent, shrinkage wasnot observed, and a residual amount was 96% after extracted by acetone.It is to be noted that a gel fraction shown by the residual amount afterextracted by acetone is represented by wt % of a residual amount incoating layer after extracted at a reflux temperature in a Soxhletextractor with acetone for 6 hours after a dried coating layer wasstripped from the glass plate. ##STR15##

POSSIBILITIES OF UTILIZATION IN INDUSTRY BY THE FOURTH ASPECT OF THEINVENTION the Invention

The low temperature-curable resin composition of the present inventioncan be readily crosslinked and cured at low temperatures of not morethan 100° C., and a cured article having a gel fraction of not less than95% can be obtained, for example, by only curing at 80° C. for 30minutes. Further, water is not required in a curing reaction or, acuring reaction proceeds by only the presence of a slight amount ofwater such as moisture in air. Still further, since a curing initiatesby volatilization of solvents, storage stability is excellent even inthe case of employing as a one-liquid composition. In curing, acomposition having a high solid content can be obtained without using acuring agent having a strong toxicity such as an isocyanate owing to alow solution viscosity in the composition. Also, since there aresimultaneously caused a variety of crosslinking reactions such as thecondensation reaction of silanol groups and the ionic polymerizationreaction of oxirane groups, and the like, the difference of curabilityin the surface and inside is small, and it is excellent in thick-layercoatability without causing shrinkage. In addition, since by-products incuring are less, there can be obtained a cured article having excellentphysical properties, in particular, the cured article is excellent inweatherability and water resistance. There can be obtained a curedarticle having excellent over-coatability, recoatability, and adhesion,etc. without the presence of uncured portions in the surface of thecured article.

TECHNICAL FIELD OF FIFTH ASPECT OF THE INVENTION

Fifth aspect of the invention relates to a thermosetting typewater-based coating composition in which there are mixed a polymer of aspecific unsaturated compound containing an epoxy group and a quaternaryammonium compound into a vinyl-based resin, and the like, in particular,it relates to a thermosetting type water-based coating composition whichis excellent in storage stability and curability in a coating layer.

BACKGROUND ART OF FIFTH ASPECT OF THE INVENTION

In a water-based coating, water is employed as a medium, and organicsolvents are not employed as a medium. Accordingly, there is not anxietysuch as a change for the worse in working surroundings and danger of afire, and it has been widely employed in a variety of fields. Forexample, as the water-based coating, there has been known a coating inwhich there is neutralized a resin composition containing apolycarboxylic acid resin having hydroxyl groups and an aminoaldehyderesin with an amine compound, followed by dispersing.

However, conventional water-based coatings require to bake attemperatures of not less than 180° C., and there is a disadvantage thatthose are poor in chemical and physical properties such as curability,weatherability, and acid resistance. Further, since viscosity of acoating-system increases in storage by gelation, practical water-basedcoatings cannot be obtained by conventional coatings in which there isemployed a bisphenol-epichlorohydrin type epoxy resin instead of theaminoaldehyde resin.

DISCLOSURE OF FIFTH ASPECT OF THE INVENTION

The present inventors, as a result of a repeated intensive investigationfor the purpose of obtaining properties well-balanced between storagestability of water-based coatings and curability of a coating layer,have found that the above-described purposes can be attained by awater-based coating composition containing a thermosetting resincomposition in which there are mixed a specific epoxy resin and aquaternary ammonium compound into a resin having hydroxyl groups andcarboxylic groups, and the present invention was completed.

That is, the present invention provides a thermosetting type water-basedcoating composition characterized by containing a resin (P) havinghydroxyl groups and carboxylic groups, an epoxy resin (Q) prepared bypolymerizing an unsaturated compound containing an alicyclic epoxy grouprepresented by the formula (6) described below, and a quaternaryammonium compound (R).

Hereinafter, the present invention will be illustrated in detail.

    R.sup.2 --O--CO--NH--CH═CH--R.sup.1                    (6)

(in the formula, R¹ represents a hydrogen atom, an aromatic hydrocarbongroup, or a saturated or unsaturated aliphatic hydrocarbon group, and R²represents formula (2) or formula (3)), ##STR16## (in the formula, R⁴and R⁵ represent a hydrogen atom, a methyl group or ethyl group,respectively, "m" is an integer of 4-8, and "n" is an integer of 1-10).

BEST MODE FOR CARRYING OUT THE FIFTH ASPECT OF THE INVENTION RESIN (P)

The resin (P) to be employed for the thermosetting type water-basedcoating composition of the present invention, if it is a resin havinghydroxyl groups and carboxylic groups, is not particularly limited. Forexample, there can be employed every conventional resins which arealready known in coating fields such as a vinyl-based resin and apolyester-based resin, and the like, which are employed as a base resin.Specifically, there can be exemplified resins described below.

(1) Vinyl-based resin As the vinyl-based resin, there can be exemplifieda copolymer of a vinyl monomer having hydroxyl group with a vinylmonomer having carboxyl group. If a vinyl monomer has hydroxyl group andcarboxyl group, there can be also employed a homopolymer thereof.

(i) As the vinyl monomer having hydroxyl group, there can be exemplifiedmonomers having hydroxyl group such as hydroxyethyl(meth)acrylate,hydroxypropyl(meth)acrylate, hydroxybutyl(meth)acrylate, apolycaprolactone diol mono(meth)acrylate, and a polyoxyethyleneglycolmono(meth)acrylate, and the like. These vinyl monomers may be employedsolely or in combination of two or more kinds. (ii) As the vinyl monomerhaving carboxyl group, there can be exemplified (meth)acrylic acid,carboxyethyl(meth)acrylate, itaconic acid, maleic acid, fumaric acid,crotonic acid, and β-carboxyethyl(meth)acrylate, and the like. Andothers, there can be also employed a modified unsaturated monocarboxylicacid such as an adduct of (meth)acrylic acid with ε-caprolactone.Herein, the modified unsaturated monocarboxylic acid has an unsaturatedgroup and carboxylic group, and if it is a modified unsaturatedmonocarboxylic acid in which a chain is extended between the unsaturatedgroup and carboxylic group, it is not particularly limited. For example,there can be exemplified a compound shown by formula (A) describedhereinafter in which (meth)acrylic acid is modified with a lactone, anunsaturated monocarboxylic acid having ester bonds such as alactone-modified compound in which terminal hydroxyl groups are modifiedwith an acid anhydride shown by formula (B) described hereinafter, and acompound having carboxyl group such as an modified unsaturatedmonocarboxylic acid having ether bond shown by formula (C) describedhereinafter.

Further, together with the vinyl monomer having carboxyl group,optionally, there can be exemplified a copolymer of a monomer having aradically polymerizable unsaturated group such as methyl(meth)acrylate,ethyl(meth)acrylate, i-propyl(meth)acrylate, n-butyl(meth)acrylate,2-ethylhexyl(meth)acrylate, acrylonitrile, acrylamide, styrene,vinyltoluene, vinylacetate, i-propylvinylether, n-butylvinylether, andmethoxyethylvinylether which do not have a functional group which reactsto hydroxyl group and carboxyl group. It is to be noted that therespective monomers may be employed solely or in combination of two ormore kinds.

    CH.sub.2 ═CR.sup.10 CO[O(CR.sup.11 R.sup.12)xCO]y-OH   Formula (A)

    CH.sub.2 ═CR.sup.10 COOCH.sub.2 CH.sub.2 O[CO(CR.sup.11 R.sup.12)xO]yCOR.sup.13 COOH                              Formula (B)

    CH.sub.2 ═CR.sup.10 COO[(CR.sup.14 R.sup.15)xO]yCOR.sup.13 COOH Formula (C)

(in the formulae, R¹⁰ represents a hydrogen atom or a methyl group, R¹¹and R¹² represent a hydrogen atom, a methyl group, or an ethyl group,respectively, and R¹³ represents a divalent aliphatic saturated orunsaturated hydrocarbon group having a carbon number of 1-10, a divalentalicyclic saturated or unsaturated hydrocarbon group having a carbonnumber of 1-6, p-xylilene group, or phenylene group, and R¹⁴ and R¹⁵represent a hydrogen atom, a methyl group, an ethyl group, a propylgroup, and a butyl group, respectively, x is an integer of 4-8, and y isan integer of 1-10)

(2) Polyester-based resin

As the polyester-based resin, there can be exemplified a polyester resinobtained by a polycondensation of polyol components such astrimethylolethane, trimethylolpropane, pentaerythritol, glycerine,ethyleneglycol, propyleneglycol, 1,3-butyleneglycol, neopentylglycol,and 1,6-hexanediol with polycarboxylic acid components such as phthalicacid(anhydride), isophthalic acid, tetrahydrophthalic acid,hexahydrophthalic acid, adipic acid, and trimellitic acid(anhydride); aresin in which the polyester resin is modified with an aliphatic acid oran epoxy resin; an acryl-grafted modified polyester resin; a modifiedpolyester resin obtained by adding acid anhydrides such as maleicanhydride to an esterified product in which a bisphenol-epichlorohydrintype epoxy resin is modified by an aliphatic acid and the like; a resinin which polycarboxylic acids and the like are added to a product inwhich a bisphenol-epichlorohydrin type epoxy resin is polymerized underthe presence of catalysts.

Of the above-described resins (P), there is particularly preferred thevinyl-based resin obtained by polymerizing a vinyl monomer havinghydroxyl group with a vinyl monomer having carboxyl group, andoptionally, other monomers.

Also, in the resins (P), a number average molecular weight is1,000-100,000, in particular, preferably 2,000-80,000, and a softeningpoint is not more than 130° C., in particular, preferably not more than115° C. Acid value is 1-100, in particular, preferably 10-80, and ahydroxyl group value is 10-5,000, in particular, preferably 20-2,000. Inthe case that the number average molecular weight is smaller than 1,000,there are apt to unpreferably lower properties in a coating layer suchas hardness, bending resistance, and corrosion resistance and, on theother hand, in the case that the number average molecular weight is morethan 100,000, there tend to become unpreferably worse outer appearancesin a coating layer such as smoothness.

Further, in the case that the softening point is higher than 130° C.,there is apt to become unpreferably worse smoothness in a coating layer.Still further, in the case that the acid value is smaller than 1, thereis apt to become unpreferably difficult a change to a water-basedproperty and, on the other hand, in the case that the acid value is morethan 100, there becomes unpreferably worse a storage stability in acoating. In the case that the hydroxyl group value is smaller than 10,there unpreferably lowers curability in a coating, and there isunpreferably observed a tendency of decline of properties in a coatinglayer such as hardness and bending resistance and, on the other hand, inthe case that the hydroxyl group value is more than 5,000, thereunpreferably lower properties in a coating layer such as waterresistance and corrosion resistance.

In the resins (P), in addition to hydroxyl group and carboxyl group,there can also be optionally introduced functional groups such as aphenolic hydroxyl group, an alkoxysilane group, and a hydroxysilanegroup. There is not particularly limited a method in order to introducethe functional groups, and already known methods can be employed. Forexample, introduction of the phenolic hydroxyl group may be conducted bycopolymerizing using a bisphenol-modified (meth)acrylate as the vinylmonomer component in the above-described vinyl-based resin, andintroduction of the alkoxysilane group and the hydroxysilane group maybe conducted by copolymerizing using a compound such asγ-methacryloxypropyl trimethoxysilane and a hydrolyzed product thereofas the vinyl monomer component in the above-described vinyl-based resin.

EPOXY RESIN (Q)

The epoxy resin (Q) to be employed in the coating composition of thepresent invention is a polymer of the unsaturated compound containing analicyclic epoxy group represented by the above-described formula (6),that is, a polymer of a compound which is prepared by the same processand, which has the same structural formula as a compound in which R² isrepresented by the formula (2) or (3) in the compound represented by theformula (1) of the first aspect of the invention. It is to be noted thatin addition to the above-described unsaturated compound containing analicyclic epoxy group, there can be also copolymerized "any one of otheralicyclic epoxy compounds containing an unsaturated group" in the secondaspect of the invention.

In the epoxy resin (Q), in addition to the unsaturated compoundcontaining an alicyclic epoxy group and the above-described othercompounds, there can be also copolymerized a radically-polymerizablemonomer containing an unsaturated group such as methyl(meth)acrylate,ethyl(meth)acrylate, i-propyl (meth)acrylate, n-butyl(meth)acrylate,2-ethylhexyl (meth)acrylate, acrylonitrile, acrylamide, styrene,vinyltoluene, vinylacetate, i-propylvinylether, n-butylvinylether, andmethoxyethylvinylether, which do not have functional groups which causea reaction with hydroxyl group and carboxyl group.

In the epoxy resin (Q), a number average molecular weight is194-100,000, particularly 194-2,000 and, in particular, preferably194-1,000, epoxy equivalent is 50-2,000 and, in particular, preferably55-1,000, a softening point is not more than 130° C. and, in particular,preferably 115° C. It is difficult to obtain a compound having a numberaverage molecular weight of smaller than 100 and, on the other hand, ina compound having a number average molecular weight of larger than100,000, since smoothness becomes worse in surface of a coated layer, itis not preferred so much. It is difficult to obtain a compound having anepoxy equivalent of smaller than 50 and, on the other hand, in acompound having an epoxy equivalent of larger than 2,000, curabilitytends to lower in a coating layer. Further, in a compound having asoftening point of higher than 130° C., smoothness is apt to becomeworse in a coating layer.

In combination with the above-described epoxy resin (Q), there can bealso employed a compound having at least two of at least one or morekinds of epoxy groups selected from an epoxy group at an alicyclichydrocarbon ring or an epoxy group which directly connects to carbonatom by which an alicyclic hydrocarbon ring is formed, in the molecule.The alicyclic hydrocarbon ring may be a small ring of a three-memberedring to a seven- or more-membered ring and, the ring may be asingle-ring or multi-ring, and further, the ring may form an organichydrocarbon ring. As specific examples of the epoxy resin (Q) to beemployed together, there can be exemplified epoxy resins havingbifunctionality or more functionalities as shown below. ##STR17## (inthe formula, "k" is an integer of 0-15, and "p" is an integer of 2-100)

In combination with the above-described epoxy resin (Q), further, therecan be also employed other epoxy resins having an epoxy group such as aglycidyl ether type epoxy resin and an aliphatic inner epoxy resin. Theother epoxy resins are preferably employed in a proportion of not morethan 25% by weight based on the total amount of both compounds from aviewpoint of storage stability of a coating and curability in a curedcoating layer.

QUATERNARY AMMONIUM COMPOUND

As the quaternary ammonium compound (R) to be employed in the coatingcomposition of the present invention, there can be employed a compoundshown by (R²⁰ R²¹ R²² R²³ N.sup.(+))X.sup.(-).

In the formula, R²⁰, R²¹, R²², and R²³ represent a hydrocarbon group,respectively, and which may be identical or different from each other.Further, the hydrocarbon group may be also substituted by hydroxylgroup. X represents a halogen ion or an anionic residual group of anacid, for example, there can be exemplified Cl, Br, F, I, SO₄, HSO₄,NO₃, PO₄ ClO₄, HCOO, CH₃ COO, and OH, and the like.

As the preferred quaternary ammonium compound (R) to be employed in thepresent invention, there can be exemplified the following compounds.

(i) There can be exemplified tetraalkyl ammonium halides such astetramethyl ammonium chloride, tetraethyl ammonium chloride, tetrabutylammonium chloride, methyltriethyl ammonium chloride, tetramethylammonium bromide, tetraethyl ammonium fluoride, and tetraethyl iodide

(ii) There can be exemplified tetraalkyl ammonium salts of an organicacid such as tetramethyl ammonium acetate and tetraethyl ammoniumformate.

(iii) There can be exemplified tetraalkyl ammonium salts of an inorganicacid such as tetramethyl ammonium hydrosulphate, tetraethyl ammoniumhydrosulphate, tetramethyl ammonium nitrate, tetraethyl ammoniumnitrate, tetraethyl ammonium perchlorate, and tetraethyl ammoniumphosphate.

(iv) There can be exemplified quaternary ammonium hydroxides such astetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide,tetrapropyl ammonium hydroxide, tetrabutyl ammonium hydroxide,tetrapentyl ammonium hydroxide, tetraisoamyl ammonium hydroxide,tetradodecyl ammonium hydroxide, methyltriethyl ammonium hydroxide,ethyltrimethyl ammonium hydroxide, decyltrimethyl ammonium hydroxide,monohydroxyethyl trimethylammonium hydroxide, monohydroxyethyltriethylammonium hydroxide, dihydroxyethyl dimethyl ammonium hydroxide,dihydroxyethyl diethyl ammonium hydroxide, trihydroxyethyl monomethylammonium hydroxide, trihydroxyethyl monoethyl ammonium hydroxide,benzyltrimethyl ammonium hydroxide, benzyltriethyl ammonium hydroxide,benzylmethyldiethyl ammonium hydroxide, and cyclohexyltrimethyl ammoniumhydroxide.

Of those, the quaternary ammonium hydroxides are particularly preferredin view of readily dispersing the resin (P) and the epoxy resin (Q) intowater, and providing a coating composition having an excellent storagestability, and moreover, capability of forming a coating layer which isexcellent in water resistance and corrosion resistance.

THERMOSETTING TYPE WATER-BASED COATING COMPOSITION

In the thermosetting type water-based coating composition of the presentinvention, the resin (P) is mixed in 40-97% by weight, preferably 50-95%by weight, and more preferably, 60-90% by weight, and the epoxy resin(Q) is mixed in 3-60% by weight, preferably 5-50% by weight, and morepreferably, 10-40% by weight based on the total amount of the resin (P)and the epoxy resin (Q). In the case that the resin (P) is less than 40%by weight and the epoxy resin (Q) is more than 60% by weight,dispersibility into water lowers in a coating composition obtained. Onthe other hand, in the case that the resin (P) is more than 97% byweight and the epoxy resin (Q) is less than 3% by weight, there lowerproperties in a coating layer such as water resistance, corrosionresistance, and bending resistance.

Also, the epoxy resin (Q) is preferably mixed with the resin (P), sothat an equivalent ratio (hydroxyl groups/epoxy groups) of hydroxylgroups in the resin (P) becomes not less than 0.3, preferably, 0.5-5,and more preferably 0.7-4 based on epoxy groups in the epoxy resin (Q).In the case that the equivalent ratio is less than 0.3, unreactedcomponents in the resin (P) become large in a coating layer, resultingin that there occasionally lower properties in a coating layer such asbending resistance, water resistance, and corrosion resistance. Further,the epoxy resin (Q) can be stably dispersed into water by carboxylgroups in the resin (P), and mixing proportion thereof is a range of0.1-1, particularly, preferably 0.1-0.6 as an equivalent ratio ofcarboxyl groups to epoxy groups from a viewpoint of dispersion intowater and storage stability of a coating. The quaternary ammoniumcompound (R) is preferably employed in a range of 0.01-10% by weight,preferably 0.1-7% by weight, and more preferably, 0.1-5% by weight basedon the total amount of the resin (P), the epoxy resin (Q), and thequaternary ammonium compound (R). In the range, there can be obtained aresin having sufficient weatherability and acid resistance.

As a method for the preparation of the thermosetting type water-basedcoating composition of the present invention, the following methods areexemplified.

First of all, the epoxy resin (Q) or a solution in which the epoxy resin(Q) is dissolved or dispersed in an organic solvent is mixed into asolution in which the resin (P) is dissolved or dispersed in an organicsolvent. Subsequently, the quaternary ammonium compound (R) andoptionally a neutralizing agent are mixed into a mixture obtained,followed by dispersing into water to prepare. As organic solvents to beemployed in order to dissolve or disperse the above-described resin (P)or the epoxy resin (Q), there is preferred an organic solvent which issubstantially inert to functional groups in the resins and,specifically, there are exemplified alcohol-based solvents, ether-basedsolvents, ketone-based solvents, ester-based solvents, andhydrocarbon-based solvents, and the like. Of those, there are preferablyemployed hydrophilic solvents such as alcohol-based solvents andether-based solvents as a main solvent. Further, as the neutralizingagent, there can be employed, for example, ammonia, trimethylamine,triethylamine, tributylamine, dimethylethanol amine,diethylethanolamine, dimethylpropanolamine, methyldiethanol amine,ethyldiethanol amine, and triethanol amine, and the like. It is to benoted that in the case that the quaternary ammonium hydroxide isemployed as the quaternary ammonium compound (R), resin components canbe dispersed into water without the use of the neutralizing agent.

Also, there may be optionally employed the quaternary ammonium compound(R) in combination with the above-described neutralizing agents.

In the coating composition of the present invention, there can be mixedother compounds. As resins to be mixed, there can be also mixed a polyolresin not containing carboxylic groups such as a polytetramethyleneglycol, a bisphenol A-ethyleneoxide adduct, a polycaprolactone polyol, apolycarbonatediol, a polyurethane polyol, a vinylalcohol (co)polymer,and a styrene-allylalcohol copolymer. As a catalyst for the purpose ofcuring a coating layer at lower temperatures, there can be exemplified aphenol compound such as catechol, a silanol compound such asdiphenylsilanediol, a metallic chelating compound composed of chelatingcompounds of metals such as Al, Ti, V, Fe, Zn, Zr, and Sn withβ-diketone such as acetoethylacetate, trifluoroacetyl acetone, anddibenzoylacetyl acetone. The catalyst is preferably mixed within a rangeof 0.01-10 parts by weight based on 100 parts by weight of the totalamount of the resin (P) and the epoxy resin (Q). Further, there can beoptionally mixed coloring pigments such as a Titanium White, CarbonBlack, and red iron oxide, extender pigments such as clay, talc, andsilica, dispersants for pigments, an anti-repelling agent, a fluiditymodifier, and the like, which are additives for coatings.

There is not particularly limited a method for forming a coating layerusing the coating composition of the present invention. For example, itcan be conducted by coating on the surface of a base material by a meanssuch as an electro-deposition coating, a spray coating, an immersioncoating, a roller coating, and brush coating, followed by drying.

Thickness of coating layer is not particularly limited, and it isusually sufficiently employed within a range of 10-100 μm.

Drying of the coating layer can be preferably conducted in a range of0-200° C., and more preferably 50-180° C. It can be conducted at 120° C.for 30 minutes or so, and at 180° C. for 10 minutes or so. The basematerial to be coated is not also particularly limited, and there can bepreferably employed a wide range of metals such as a steel, aluminum,Alumite, copper, a metal-plated steel in which the surface is plated byzinc, chromium, and aluminum, and the like, a steel in which the surfaceof an iron is chemically-treated by chromic acid and phosphoric acid, orelectrolytically-treated.

EXAMPLES OF FIFTH ASPECT OF THE INVENTION

Hereinafter, although the present invention is specifically illustratedby Examples, the present invention is not limited by those. It is to benoted that "part" represents "part by weight" except a case particularlyshown, and "%" represents "% by weight" except a case particularlyshown.

Method for measurements

(1) Storage Stability: A state of sedimentation and separation in adispersed product was visually observed after placing for 1 month at 30°C., and a case was judged as no-abnormal, in which there is not caused acolor change by sedimentation of a dispersant in a coating composition.

(2) Smoothness in a coating layer: An uneven state of the surface in acoating layer was visually observed, and a case was judged excellent, inwhich gloss exists in the surface.

(3) Salt spray resistance: It was tested according to JIS Z-2371, therewas judged qualified a sample having a creep width of not exceeding 2 mmin one side from a cut portion in a coating layer. Test time was 1000hours.

(4) Pencil hardness: It was tested according to JISK-5400.

(5) Bending resistance: A test plate was bent at a right angle within1-2 seconds at an atmosphere of 20° C., and there was judged qualifiedthe absence of abnormality such as peel or crack of a coating layer in abent portion.

(6) Gel fraction: A dried coating layer was stripped and put in anet-like vessel having 300 mesh made by a stainless steel, and anextraction was conducted by a soxhlet extractor at a reflux temperaturefor 6 hours using a mixed solvent of acetone/methanol=1/1, followed bycalculating the gel fraction according to the following equation. Gelfraction (%) was evaluated by "the weight of coating layer after beingextracted"/"the weight of coating layer before being extracted".

Example 1

A 4-necked flask was charged with 75 parts of methyl propanol, followedby heating to 110° C. Into the flask, there were added dropwise over 1hour a mixture composed of 3 parts of acrylic acid, 20 parts ofhydroxyethylacrylate, 57 parts of methylmethacrylate, and 20 parts ofstyrene, and a mixture composed of 1 part of 2,2'-azobisisobutylnitrileand 5 parts of methylisobutyl ketone. Aging was conducted for 1.5 hourto obtain a resin solution (P) having an acid value of 23, a hydroxylvalue of 97, a number average molecular weight of 20000, and the solidcontent of 55%. Subsequently, a 4-necked flask was charged with 25 partsof methylpropanol, followed by heating to 110° C., and followed byadding dropwise a mixture composed of 25 parts of the compound (S)described below, a mixture composed of 5 parts of2,2'-azobisisobutylnitrile and 5 parts of methylisobutyl ketone over 3hours. Aging was further conducted for 3 hours to obtain a resinsolution (Q) having an epoxy equivalent of 200, an average molecularweight of approximately 3,000, and the solid content of 42%. 19.5 partsof 20% solution of tetraethyl ammonium hydroxide was added into 181parts of the above-described resin solution (P) and 60 parts of the (Q),followed by adding 166 parts of a deionized water while agitating toobtain a water-dispersed product having the solid content of 30% and anaverage particle size of 0.15 μm. The storage stability in thewater-dispersed product obtained was not abnormal in both of a coatingsstate and properties of a coating layer. Further, the water-dispersedproduct before the storage stability test was coated in the thickness ina dried layer of 20 μm by spraying on a steel plate treated by zincphosphate, followed by drying at 80° C. for 10 minutes and furtherdrying at 120° C. for 20 minutes to obtain a coated product. In thecoated product, the smoothness of a coating layer was excellent, and thesalt spray resistance was also passed, the pencil hardness was H, andthe bending resistance was also passed. The gel fraction in the coatinglayer was 97%. ##STR18##

Example 2

A 4-necked flask was charged with 64 parts of methylpropanol, followedby heating to 110° C. Into the flask, there were added dropwise over 1hour a mixture composed of 4 parts of methacrylic acid, 25 parts ofhydroxyethylmethacrylate, 10 parts of 2-ethylhexyl methacrylate, 51parts of methylmethacrylate, and 10 parts of styrene, and a mixturecomposed of 1 part of 2,2'-azobisisobutylnitrile and 5 parts ofmethylisobutyl ketone. Aging was further conducted for 1.5 hour toobtain a resin solution (P) having an acid value of 26, a hydroxyl valueof 108, a number average molecular weight of 25,000, and the solidcontent of 59%. Subsequently, a 4-necked flask was charged with 25 partsof methylpropanol, followed by heating to 110° C., and followed byadding dropwise a mixture composed of 10 parts of the above-describedcompound (S) and 5 parts of the compound (T) described below, and amixture composed of 5 parts of 2,2'-azobisisobutylnitrile and 5 parts ofmethylisobutyl ketone over 3 hours. Aging was further conducted for 3hours to obtain a resin solution (Q) having an epoxy equivalent of 200,an average molecular weight of approximately 3,000, and the solidcontent of 30%. 16.2 parts of 10% solution of tetramethyl ammoniumhydroxide was added into 170 parts of the above-described resin solution(P) and 60 parts of the (Q), followed by adding 148 parts of a deionizedwater while agitating to obtain a water-dispersed product having thesolid content of 30% and an average particle size of 0.18μ. The storagestability of the water-dispersed product obtained was not abnormal inboth of a coatings state and properties of a coating layer. Thewater-dispersed product before the storage test was likewise coated anddried to obtain a coated product, and the smoothness of a coating layerin the coated product was excellent, and the salt spray resistance wasalso passed, the pencil hardness was 3H, and the bending resistance alsopassed. It is to be noted that the gel fraction in the coating layer was97%. ##STR19##

Example 3

160 parts of a deionized water was added into a mixture composed of 150parts of 55%-resin solution (P) obtained in the Example 1, 10 parts of42%-resin solution (Q) obtained in the Example 1, 10 parts of3,4-epoxycyclohexylcarboxymethyl cyclohexeneoxide, 17.9 parts of10%-solution of tetrabutyl ammonium hydroxide, and 2 parts oftriethylamine while agitating to obtain a water-dispersed product havingthe solid content of 27% and an average particle size of 0.1 μm. Thestorage stability in the water-dispersed product obtained was notabnormal in both of a coatings state and properties of a coating layer.Further, the water-dispersed product before the storage stability testwas coated in the thickness of 20 μm in a dried layer by spraying onto asteel plate treated by zinc phosphate, followed by drying at 80° C. for10 minutes and further drying at 140° C. for 20 minutes to obtain acoated product. In the coated product, the smoothness of a coating layerwas excellent, and the salt spray resistance was also passed, the pencilhardness was 2H, and the bending resistance also passed. It is to benoted that the gel fraction in the coating layer was 93%.

Comparative Example 1

The same procedures were followed as in the Example 1 except that 20parts of hydroxyethylacrylate and 57 parts of methylmethacrylate in theExample 1 were changed to 77 parts of methylmethacrylate, and 19.5 partsof 20% solution of tetrahydroxy ammonium hydroxide was changed to 3.4parts of triethylamine, respectively, and 166 parts of a deionized waterin the Example 1 was changed to 180 parts to obtain a water-dispersedproduct having the solid content of 30%. The storage stability was notabnormal in the water-dispersed product obtained. Further, thewater-dispersed product before storage was likewise coated and dried asin the Example 1 to obtain a coated product. Although the smoothness ofa coating layer was excellent in the coated product, the salt sprayresistance did not pass, and the pencil hardness was 4B, and the bendingresistance did not also pass. It is to be noted that the gel fraction inthe coating layer was 55%.

POSSIBILTIES OF UTILIZATION IN INDUSTRY BY THE FIFTH ASPECT OF THEINVENTION

In the thermosetting type water-based coating composition of the presentinvention, there does not almost proceed a reaction of functional groupsthemselves which are hydroxyl groups in the resin (P) and epoxy groupsin the epoxy resin (Q) at the vicinity of room temperatures, and when itis baked at the vicinity of 100° C., there abruptly proceeds thereaction of functional groups themselves. Therefore, it is particularlyexcellent in the storage stability and a low-temperature curability of acoating layer. Also, the smoothness is excellent in a cured coatinglayer formed from the thermosetting type water-based coating compositionof the present invention, and it is excellent in the salt sprayresistance and the bending resistance.

What is claimed is:
 1. A compound represented by formula (1),

    R.sup.2 --O--CO--NH--CH═CH--R.sup.1                    ( 1)

wherein R¹ represents a hydrogen atom, an aromatic hydrocarbon group, ora saturated or unsaturated aliphatic hydrocarbon group, and wherein R²represents an aliphatic hydrocarbon group having a reactive functionalgroup for thermosetting or photocuring.
 2. A compound as claimed inclaim 1, wherein said group containing a reactive functional group is agroup containing an alicyclic epoxide.
 3. A compound as claimed in claim1, wherein said aliphatic hydrocarbon group substituted by a groupcontaining a reactive functional group is a group represented by formula(2) or (3), ##STR20## wherein R⁴ and R⁵ represent a hydrogen atom, amethyl group or ethyl group, respectively, "m" is an integer of 4-8, and"n" is an integer of 1-10.
 4. A polymer of a compound as claimed in anyone of claims 1-3.
 5. A process for the preparation of a compound asclaimed in claim 1 which comprises allowing to react a compound having ahydroxyl group represented by formula (4-1) or (4-2) with a compoundrepresented by formula (5), ##STR21## wherein R⁴ and R⁵ represent ahydrogen atom, a methyl group or ethyl group, respectively, "m" is aninteger of 4-8, and "n" is an integer of 1-10,

    N.sub.3 --CO--CH═CH--R.sup.1                           ( 5)

wherein R¹ represents a hydrogen atom, an aromatic hydrocarbon group, ora saturated or unsaturated aliphatic hydrocarbon group.
 6. An activeenergy ray-curable type unsaturated resin composition which comprisesmixing a reaction product of an unsaturated compound containing analicyclic epoxy group represented by formula (6) with an unsaturatedresin containing acid groups, with a diluent,

    R.sup.2 --O--CO--NH--CH═CH--R.sup.1                    ( 6)

wherein R¹ represents a hydrogen atom, an aromatic hydrocarbon group, ora saturated or unsaturated aliphatic hydrocarbon group, R² representsformula (2) or formula (3), ##STR22## wherein R⁴ and R⁵ represent ahydrogen atom, a methyl group or ethyl group, respectively, "m" is aninteger of 4-8, and "n" is an integer of 1-10.
 7. An active energyray-curable type unsaturated resin composition as clamed in claim 6,wherein said unsaturated resin containing acid groups is anacrylic-based resin containing acid groups.
 8. An alkali developable andactive energy ray-curable type resist resin composition which comprisesan active energy ray-curable type unsaturated resin composition asclaimed in claim 6 or
 7. 9. An active energy ray-polymerizableunsaturated resin composition obtainable by allowing to react anunsaturated compound (E) containing an alicyclic epoxy group representedby formula (6) with a colloidal silica (F) in the presence of a metalchelate and/or metal alkoxide (G),

    R.sup.2 --O--CO--NH--CH═CH--R.sup.1                    ( 6)

wherein R¹ represents a hydrogen atom, an aromatic hydrocarbon group, ora saturated or unsaturated aliphatic hydrocarbon group, R² representsformula (2) or formula (3), ##STR23## wherein R⁴ and R⁵ represent ahydrogen atom, a methyl group or ethyl group, respectively, "m" is aninteger of 4-8, and "n" is an integer of 1-10.
 10. A powder-state activeenergy ray-polymerizable unsaturated resin composition obtained byremoving a solvent from an active energy ray-polymerizable unsaturatedresin composition as claimed in claim
 9. 11. An active energyray-curable composition which comprises an active energyray-polymerizable unsaturated resin composition as claimed in claim 9.12. A powder-state active energy ray-curable composition which comprisesa powder-state active energy ray-polymerizable unsaturated resincomposition as claimed in claim
 10. 13. A low temperature-curable resincomposition characterized by containing the following components (a),(b), and (c),(a) a vinyl copolymer having a number average molecularweight of 2,000-100,000 which is a copolymer of a polysiloxane-basedmacromonomer having a number average molecular weight of 400-50,000containing at least two hydroxyl groups or alkoxyl groups in themolecule with a vinyl monomer containing oxirane group represented byformula (6), said macromonomer being obtained by allowing to react70-99.999% by mol of a compound (H) represented by formula (7) with30-0.001% by mol of a compound (J) represented by formula (8), (b) a6-coordinated organic aluminum chelate compound and/or an 8-coordinatedorganic zirconium chelate compound, (c) a compound having a numberaverage molecular weight of not more than 1,000 containing at least twoalicyclic oxirane groups in the molecule,

    R.sup.11 --SiR.sup.12 R.sup.13 R.sup.14                    ( 7)

wherein R¹¹ represents an aliphatic hydrocarbon group having a carbonnumber of 1-8 or a phenyl group, R¹², R¹³, and R¹⁴ represent an alkoxylgroup having a carbon number of 1-4 or a hydroxyl group,

    CH.sub.2 ═CR.sup.15 COO(CH.sub.2).sub.k --SiR.sup.16 R.sup.17 R.sup.18 ( 8)

wherein R¹⁵ represents a hydrogen atom or a methyl group, R¹⁶, R¹⁷, andR¹⁸ represent any one of a hydroxyl group, an alkoxyl group having acarbon number of 1-4, and an aliphatic hydrocarbon group having a carbonnumber of 1-8, "k" is an integer of 1-6, and all the R¹⁶, R¹⁷, and R¹⁸are not simultaneously an aliphatic hydrocarbon group having a carbonnumber of 1-8,

    R.sup.2 --O--CO--NH--CH═CH--R.sup.1                    ( 6)

wherein R¹ represents a hydrogen atom, an aromatic hydrocarbon group, ora saturated or unsaturated aliphatic hydrocarbon group, and R²represents formula (2) or formula (3), ##STR24## wherein R⁴ and Rrepresent a hydrogen atom, a methyl group or ethyl group, respectively,"m" is an integer of 4-8, and "n" is an integer of 1-10.
 14. Athermosetting type water-based coating composition characterized bycontaining the following components (P), (Q), and (R),(P) a resin havinghydroxyl groups and carboxylic groups, (Q) an epoxy resin prepared bypolymerizing an unsaturated compound containing an alicyclic epoxy grouprepresented by the formula (6) as claimed in claim 13, (R) a quaternaryammonium compound.